U.S. patent number 5,795,930 [Application Number 08/464,605] was granted by the patent office on 1998-08-18 for water insoluble ammonium polyphosphate powder for flame-retardant thermoplastic polymer composition.
This patent grant is currently assigned to Chisso Corporation. Invention is credited to Tikashi Fukumura, Kouji Inoue, Masuo Iwata, Noriaki Narita, Mika Seki, Ryoji Takahashi, Masaya Tanaka.
United States Patent |
5,795,930 |
Fukumura , et al. |
August 18, 1998 |
**Please see images for:
( Certificate of Correction ) ** |
Water insoluble ammonium polyphosphate powder for flame-retardant
thermoplastic polymer composition
Abstract
A flame-retardant thermoplastic polymer composition which
inhibits the bleeding of ammonium polyphosphate onto the surface of
a molded article include components (A), (B), (C), and (D), wherein
includes an oxygen-containing solid compound containing an element
of Group II, Group III or Group IV of the periodic table, (B)
includes a triazine ring-containing organic compound, (C) includes
an ammonium polyphosphate powder, a melamine-coated ammonium
polyphosphate powder and a powder of a water-insolubilized,
melamine-coated ammonium polyphosphate powder, and (D) includes a
thermoplastic polymer.
Inventors: |
Fukumura; Tikashi (Kitakyushu,
JP), Iwata; Masuo (Yokohama, JP), Narita;
Noriaki (Yokohama, JP), Inoue; Kouji (Yokohama,
JP), Tanaka; Masaya (Kitakyushu, JP), Seki;
Mika (Yokohama, JP), Takahashi; Ryoji (Tokyo,
JP) |
Assignee: |
Chisso Corporation (Osaka,
JP)
|
Family
ID: |
27307371 |
Appl.
No.: |
08/464,605 |
Filed: |
August 3, 1995 |
PCT
Filed: |
December 28, 1994 |
PCT No.: |
PCT/JP94/02294 |
371
Date: |
August 03, 1995 |
102(e)
Date: |
August 03, 1995 |
Foreign Application Priority Data
|
|
|
|
|
Dec 28, 1993 [JP] |
|
|
5-354089 |
Dec 28, 1993 [JP] |
|
|
5-354672 |
Apr 6, 1994 [JP] |
|
|
6-93721 |
|
Current U.S.
Class: |
524/100; 524/416;
524/96; 524/430; 524/437 |
Current CPC
Class: |
C08K
5/16 (20130101); C08K 5/3492 (20130101); C08K
9/04 (20130101); C08K 3/22 (20130101); C08K
3/32 (20130101); C08K 9/04 (20130101); C08L
63/00 (20130101) |
Current International
Class: |
C08K
5/00 (20060101); C08K 5/16 (20060101); C08K
5/3492 (20060101); C08K 9/04 (20060101); C08K
9/00 (20060101); C08K 3/00 (20060101); C08K
3/32 (20060101); C08K 3/22 (20060101); C08K
009/04 (); C08K 034/92 () |
Field of
Search: |
;524/416,100,101,96,436,430,437 ;252/607,609 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
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|
0014463 |
|
Aug 1980 |
|
EP |
|
0180795 |
|
May 1986 |
|
EP |
|
326082 |
|
Aug 1989 |
|
EP |
|
0614936 |
|
Sep 1994 |
|
EP |
|
4146944 |
|
May 1992 |
|
JP |
|
4142352 |
|
May 1992 |
|
JP |
|
4142348 |
|
May 1992 |
|
JP |
|
4139241 |
|
May 1992 |
|
JP |
|
5310997 |
|
Nov 1993 |
|
JP |
|
5331322 |
|
Dec 1993 |
|
JP |
|
Other References
English Abstract of Japanese Patent No. JP 1268738, Oct. 26, 1989.
.
English Abstract of Japanese Patent No. JP 3009937, Jan. 17, 1991.
.
English Abstract of Japanese Patent No. JP 61103962, May 22, 1986.
.
English Abstract of Japanese Patent No. JP 77039930, Oct.
07,1977..
|
Primary Examiner: Hoke; Veronica P.
Attorney, Agent or Firm: Leydig, Voit & Mayer, Ltd.
Claims
What is claimed is:
1. A flame-retardant thermoplastic polymer composition
comprising;
(A) a solid oxygen-containing metal compound including at least one
element selected from the group consisting of Ca, Ba, Sr, Mg, Al,
Si, Zn, Cd, Ti, Zr and Sn, and wherein said solid oxygen-containing
metal compound is at least one compound selected from the group
consisting of a hydroxide, a basic carbonate, a carbonate, a
carbonate hydrate, a silicate, a silicate hydrate, an oxide, and an
oxide hydrate, said solid oxygen-containing metal compound in an
amount of 0.1 to 5% by weight,
(B) a nitrogen-containing organic compound selected from the group
consisting of a homopolymer and a copolymer, wherein each of said
homopolymer and said copolymer comprises units represented by the
following formula (II): ##STR4## wherein X and Z.sup.1 are each a
group bonded to a triazine skeleton through a nitrogen atom; X is
an alkylamino group represented by --NHR.sup.1 or --NR.sup.2
R.sup.3, wherein R.sup.1, R.sup.2 and R.sup.3 are each
independently a linear or branched alkyl group having 1 to 6 carbon
atoms, a morpholino group, a piperidino group or a
hydroxyalkylamino group represented by --NHR.sup.4 or --NR.sup.5
R.sup.6, wherein R.sup.4, R.sup.5 and R.sup.6 are each
independently a linear or branched hydroxyalkyl group having 2 to 6
carbon atoms; and Z.sup.1 is a divalent group selected from the
group consisting of piperazine, --HN(CH.sub.2).sub.m NH-- wherein m
is a number of 2 to 6, and --NR.sup.7 (CH.sub.2).sub.n R.sup.8 N--
wherein n is a number of 2 to 6, and wherein one of said R.sup.7
and R.sup.8 is a hydroxyethyl group, said nitrogen-containing
compound in an amount of 0.1 to 20% by weight,
(C) at least one powder selected from the group consisting of a
melamine-coated ammonium polyphosphate powder obtained by adding or
adsorbing melamine on surfaces of ammonium polyphosphate powder to
chemically link a melamine coating to the ammonium polyphosphate
powder via an oxygen-proton bond of a polyphosphoric acid derived
from the ammonium polyphosphate powder, and a water-insoluble
ammonium polyphosphate powder obtained by adding or adsorbing
melamine on surfaces of ammonium polyphosphate powder to chemically
link a melamine coating to the ammonium polyphosphate powder via an
oxygen-proton bond of a polyphosphoric acid derived from the
ammonium polyphosphate powder, and reacting an active hydrogen on
an amine group of the melamine with a crosslinking agent having a
functional group reactive to said active hydrogen to produce a
crosslinked structure in the melamine coating, said at least one
powder in an amount of 10 to 40% by weight, and
(D) a thermoplastic polymer in an amount of 35 to 88.9% by weight,
the total amount of said components (A), (B), (C) and (D) being
100% by weight.
2. The flame-retardant thermoplastic polymer composition as claimed
in claim 1, wherein the oxygen-containing metal compound has a mean
particle diameter of not more than 10 .mu.m.
3. The flame-retardant thermoplastic polymer composition as claimed
in claim 1, wherein the nitrogen-containing organic compound is a
product obtained by the reaction of cyanuric chloride with
diamine.
4. The flame-retardant thermoplastic polymer composition
of claim 1, wherein the thermoplastic polymer (D) is at least one
selected from the group consisting of 1-olefin homopolymer resins,
1-olefin copolymer resins, polymer resins of vinyl monomers or
their derivatives, polyamide resins, mixtures of different
polyamide resins, homopolymer resins of aromatic compounds,
copolymer resins of aromatic compounds, mixtures of homopolymer and
copolymer resins of aromatic compounds, thermoplastic elastomers,
mixtures of different thermoplastic elastomers, elastomers,
mixtures of different elastomers, addition polymerized elastomers,
and condensation polymerized elastomers.
5. The flame-retardant thermoplastic polymer compositions as
claimed in claim 1, wherein the thermoplastic polymer is at least
one polymer selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
6. A flame-retardant thermoplastic polymer composition
comprising:
(B) a nitrogen-containing organic compound selected from the group
consisting of a homopolymer and a copolymer, wherein each of said
homopolymer and said copolymer comprises constituent units
represented by the following formula (II): ##STR5## wherein each of
X and Z.sup.1 has a structure bonded to a triazine ring through a
nitrogen atom; X is an alkylamino group represented by --NHR.sup.1
or --NR.sup.2 R.sup.3, wherein R.sup.1, R.sup.2 and R.sup.3 are
each independently a linear or branched alkyl group having 1 to 6
carbon atoms, a morpholino group, a piperidino group or a
hydroxyalkylamino group represented by at least one of --NHR.sup.4
and --NR.sup.5 R.sup.6 wherein R.sup.4, R.sup.5 and R.sup.6 are
each independently a linear or branched hydroxyalkyl group having 2
to 6 carbon atoms; and Z.sup.1 is selected from the group
consisting of piperazinylene, --NH(CH.sub.2).sub.m NH-- wherein m
is a number of 2 to 6, and --NR.sup.7 (CH.sub.2).sub.n R.sup.8 N--
wherein n is a number of 2 to 6, and wherein one of said R.sup.7
and R.sup.8 is a hydroxyethyl group, said nitrogen-containing
compound in an amount of 1 to 20% by weight,
(C) a water-insoluble ammonium polyphosphate powder in an amount of
10 to 40% by weight, said water-insoluble ammonium polyphosphate
powder being obtained by adding or adsorbing melamine on surfaces
of the ammonium polyphosphate particles to chemically link a
melamine coating to the ammonium polyphosphate particles via an
oxygen-proton bond of a polyphosphoric acid derived from the
ammonium polyphosphate particles, and reacting an active hydrogen
attached to an amino group of the melamine with a crosslinking
agent having a functional group reactive to said active hydrogen to
produce a crosslinked structure in the melamine coating, and
(D) a thermoplastic polymer in an amount of 40 to 89% by
weight,
the total amount of said components (B), (C) and (D) being 100% by
weight.
7. The flame-retardant thermoplastic polymer composition of claim
6, wherein the crosslinking agent includes at least one selected
from the group consisting of an isocyanate group, a glycidyl group,
a carboxyl group, a methylol group and an aldehyde group.
8. The flame-retardant thermoplastic polymer composition as claimed
in claim 6, wherein said added or adsorbed melamine is in an amount
of 0.5 to 20% by weight based on said ammonium polyphosphate
particles.
9. The flame-retardant thermoplastic polymer compositions as
claimed in claim 6, wherein the thermoplastic polymer (D) is at
least one selected from the group consisting of aliphatic
thermoplastic resins, aromatic thermoplastic resins, aliphatic
elastomers, aromatic elastomers, mixtures different elastomers, and
mixtures of thermoplastic resins and elastomers or partially
cross-linked elastomers.
10. The flame-retardant thermoplastic polymer composition
of claim 9, wherein the thermoplastic polymer (D) is at least one
selected from the group consisting of 1-olefin homopolymer resins,
1-olefin copolymer resins, polymer resins of vinyl monomers or
their derivatives, polyamide resins, mixtures of different
polyamide resins, homopolymer resins of aromatic compounds,
copolymer resins of aromatic compounds, mixtures of homopolymer and
copolymer resins of aromatic compounds, thermoplastic elastomers,
mixtures of different thermoplastic elastomers, elastomers,
mixtures of different elastomers, addition polymerized elastomers,
and condensation polymerized elastomers.
11. The flame-retardant thermoplastic polymer compositions as
claimed in claim 5, wherein the thermoplastic polymer is at least
one polymer selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
12. The flame-retardant thermoplastic polymer composition of claim
2, wherein the nitrogen-containing organic compound is a product
obtained by the reaction of cyanuric chloride with diamine.
13. The flame-retardant thermoplastic polymer composition of claim
2, wherein the thermoplastic polymer (D) is
at least one selected from the group consisting of 1-olefin
homopolymer resins, 1-olefin copolymer resins, polymer resins of
vinyl monomers or their derivatives, polyamide resins, mixtures of
different polyamide resins, homopolymer resins of aromatic
compounds, copolymer resins of aromatic compounds, mixtures of
homopolymer and copolymer resins of aromatic compounds,
thermoplastic elastomers, mixtures of different thermoplastic
elastomers, elastomers, mixtures of different elastomers, addition
polymerized elastomers, and condensation polymerized
elastomers.
14. The flame-retardant thermoplastic polymer composition of claim
6 wherein the thermoplastic polymer (D) is
at least one selected from the group consisting of 1-olefin
homopolymer resins, 1-olefin copolymer resins, polymer resins of
vinyl monomers or their derivatives, polyamide resins, mixtures of
different polyamide resins, homopolymer resins of aromatic
compounds, copolymer resins of aromatic compounds, mixtures of
homopolymer and copolymer resins of aromatic compounds,
thermoplastic elastomers, mixtures of different thermoplastic
elastomers, elastomers, mixtures of different elastomers, addition
polymerized elastomers, and condensation polymerized
elastomers.
15. The flame-retardant thermoplastic polymer composition of claim
2, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene, poly(meth)acrylic
acid resins, poly(meth)acrylic acid derivative resins, polyvinyl
chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
16. The flame-retardant thermoplastic polymer composition of claim
5, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene, poly(meth)acrylic
acid resins, poly(meth)acrylic acid derivative resins, polyvinyl
chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
17. The flame-retardant thermoplastic polymer composition of claim
12, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene, poly(meth)acrylic
acid resins, poly(meth)acrylic acid derivative resins, polyvinyl
chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
18. The flame-retardant thermoplastic polymer composition of claim
4, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene, poly(meth)acrylic
acid resins, poly(meth)acrylic acid derivative resins, polyvinyl
chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
19. The flame-retardant thermoplastic polymer composition of claim
13 wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene, poly(meth)acrylic
acid resins, poly(meth)acrylic acid derivative resins, polyvinyl
chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
20. The flame-retardant thermoplastic polymer composition of claim
14, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene, poly(meth)acrylic
acid resins, poly(meth)acrylic acid derivative resins, polyvinyl
chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
21. The flame-retardant thermoplastic polymer composition of claim
7, wherein said added or absorbed melamine is in an amount of 0.5
to 20% by weight based on said ammonium polyphosphate
particles.
22. The flame-retardant thermoplastic polymer composition of claim
7, wherein the thermoplastic polymer (D) is at least one selected
from the group consisting of aliphatic thermoplastic resins,
aromatic thermoplastic resins, aliphatic elastomers, aromatic
elastomers, mixtures different elastomers, and mixtures of
thermoplastic resins and elastomers or partially cross-linked
elastomers.
23. The flame-retardant thermoplastic polymer composition of claim
8, wherein the thermoplastic polymer (D) is at least one selected
from the group consisting of aliphatic thermoplastic resins,
aromatic thermoplastic resins, aliphatic elastomers, aromatic
elastomers, mixtures different elastomers, and mixtures of
thermoplastic resins and elastomers or partially cross-linked
elastomers.
24. The flame-retardant thermoplastic polymer composition of claim
21, wherein the thermoplastic polymer (D) is at least one selected
from the group consisting of aliphatic thermoplastic resins,
aromatic thermoplastic resins, aliphatic elastomers, aromatic
elastomers, mixtures different elastomers, and mixtures of
thermoplastic resins and elastomers or partially cross-linked
elastomers.
25. The flame-retardant thermoplastic polymer composition of claim
7, wherein the thermoplastic polymer (D)
is at least one selected from the group consisting of 1-olefin
homopolymer resins, 1-olefin copolymer resins, polymer resins of
vinyl monomers or their derivatives, polyamide resins, mixtures of
different polyamide resins, homopolymer resins of aromatic
compounds, copolymer resins of aromatic compounds, mixtures of
homopolymer and copolymer resins of aromatic compounds,
thermoplastic elastomers, mixtures of different thermoplastic
elastomers, elastomers, mixtures of different elastomers, addition
polymerized elastomers, and condensation polymerized
elastomers.
26. The flame-retardant thermoplastic polymer composition of claim
8, wherein the thermoplastic polymer (D)
is at least one selected from the group consisting of 1-olefin
homopolymer resins, 1-olefin copolymer resins, polymer resins of
vinyl monomers or their derivatives, polyamide resins, mixtures of
different polyamide resins, homopolymer resins of aromatic
compounds, copolymer resins of aromatic compounds, mixtures of
homopolymer and copolymer resins of aromatic compounds,
thermoplastic elastomers, mixtures of different thermoplastic
elastomers, elastomers, mixtures of different elastomers, addition
polymerized elastomers, and condensation polymerized
elastomers.
27. The flame-retardant thermoplastic polymer composition of claim
21, wherein the thermoplastic polymer (D)
is at least one selected from the group consisting of 1-olefin
homopolymer resins, 1-olefin copolymer resins, polymer resins of
vinyl monomers or their derivatives, polyamide resins, mixtures of
different polyamide resins, homopolymer resins of aromatic
compounds, copolymer resins of aromatic compounds, mixtures of
homopolymer and copolymer resins of aromatic compounds,
thermoplastic elastomers, mixtures of different thermoplastic
elastomers, elastomers, mixtures of different elastomers, addition
polymerized elastomers, and condensation polymerized
elastomers.
28. The flame-retardant thermoplastic polymer composition of claim
9, wherein the thermoplastic polymer (D)
is at least one selected from the group consisting of 1-olefin
homopolymer resins, 1-olefin copolymer resins, polymer resins of
vinyl monomers or their derivatives, polyamide resins, mixtures of
different polyamide resins, homopolymer resins of aromatic
compounds, copolymer resins of aromatic compounds, mixtures of
homopolymer and copolymer resins of aromatic compounds,
thermoplastic elastomers, mixtures of different thermoplastic
elastomers, elastomers, mixtures of different elastomers, addition
polymerized elastomers, and condensation polymerized
elastomers.
29. The flame-retardant thermoplastic polymer composition of claim
21, wherein the thermoplastic polymer (D)
is at least one selected from the group consisting of 1-olefin
homopolymer resins, 1-olefin copolymer resins, polymer resins of
vinyl monomers or their derivatives, polyamide resins, mixtures of
different polyamide resins, homopolymer resins of aromatic
compounds copolymer resins of aromatic compounds, mixtures of
homopolymer and copolymer resins of aromatic compounds,
thermoplastic elastomers, mixtures of different thermoplastic
elastomers, elastomers, mixtures of different elastomers, addition
polymerized elastomers, and condensation polymerized
elastomers.
30. The flame-retardant thermoplastic polymer composition of claim
28, wherein the thermoplastic polymer (D)
is at least one selected from the group consisting of 1-olefin
homopolymer resins, 1-olefin copolymer resins, polymer resins of
vinyl monomers or their derivatives, polyamide resins, mixtures of
different polyamide resins, homopolymer resins of aromatic
compounds, copolymer resins of aromatic compounds, mixtures of
homopolymer and copolymer resins of aromatic compounds,
thermoplastic elastomers, mixtures of different thermoplastic
elastomers, elastomers, mixtures of different elastomers, addition
polymerized elastomers, and condensation polymerized
elastomers.
31. The flame-retardant thermoplastic polymer composition of claim
7, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
32. The flame-retardant thermoplastic polymer composition of claim
8, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
33. The flame-retardant thermoplastic polymer composition of claim
21, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
34. The flame-retardant thermoplastic polymer composition of claim
9, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
35. The flame-retardant thermoplastic polymer composition of claim
22, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
36. The flame-retardant thermoplastic polymer composition of claim
23, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
37. The flame-retardant thermoplastic polymer composition of claim
24, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
38. The flame-retardant thermoplastic polymer composition of claim
10, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
39. The flame-retardant thermoplastic polymer composition of claim
25, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
40. The flame-retardant thermoplastic polymer composition of claim
26, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
41. The flame-retardant thermoplastic polymer composition of claim
27, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
42. The flame-retardant thermoplastic polymer composition of claim
28, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
43. The flame-retardant thermoplastic polymer composition of claim
29, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
44. The flame-retardant thermoplastic polymer composition of claim
30, wherein the thermoplastic polymer is at least one polymer
selected from the group consisting of:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins,
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins,
acrylonitrile-butadiene-styrene copolymer resins,
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons, m-xylylene-adipic
acid nylons, polycarbonate resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polysulfone resins,
polyurethane resins, polyphenylene ether resins,
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein an elastomer component is
partially-crosslinked, mixtures of ethylene-propylene copolymer
elastomers and propylene resins wherein an elastomer component is
partially-crosslinked,
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers.
45. The flame-retardant thermoplastic polymer composition of claim
1, wherein the crosslinking agent includes at least one selected
from the group consisting of an isocyanate group, a glycidyl group,
a carboxyl group, a methylol group and an aldehyde group.
46. The flame-retardant thermoplastic polymer composition of claim
6, wherein said nitrogen-containing organic compound is a product
obtained by the reaction of a cyanuric chloride with a diamine.
Description
TECHNICAL FIELD
The present invention relates to a thermoplastic polymer
composition showing excellent flame retardance, more particularly
to a thermoplastic polymer composition of high flame retardance
which comprises (A) an oxygen-containing solid compound containing
an element of Group II, Group III or Group IV of the periodic
table, (B) a nitrogen-containing organic compound, (C1) an ammonium
polyphosphate powder or (C2) a melamine-coated ammonium
polyphosphate powder and (D) a thermoplastic polymer, in specific
amounts.
The present invention also relates to compositions of thermoplastic
polymers (B), which contain, in place of the component (C1) or (C2)
of the above-mentioned composition, a water-insoluble ammonium
polyphosphate powder obtained by altering the structure of a coat
of the melamine-coated ammonium polyphosphate (C2) to crosslinked
structure, and which are almost free from bleeding phenomenon even
when exposed to an atmosphere of high temperature and high humidity
and shows satisfactory flame retardance.
Furthermore, the invention relates to thermoplastic resin
compositions which are formed from at least the water-insoluble
ammonium polyphosphate powder mentioned above, (B)
nitrogen-containing organic compounds and (D) thermoplastic resins
and which are excellent in bleed resistance and flame
retardance.
Moreover, the invention relates to the water-insoluble ammonium
polyphosphate powders mentioned above (at least one kind selected
from C3, C4 and C5) and processes for preparing the same.
BACKGROUND ART
Thermoplastic polymers have been heretofore used in various fields
such as fields of industrial and domestic electrical appliances,
architecture, house furnishings, automobile parts, etc., because
they are advantageous in sanitary viewpoint, processability,
chemical resistance, weathering resistance, electrical properties
and mechanical strength. Moreover, the use application of the
thermoplastic polymers has been extended. With extension of their
use application, flame retardance has been required for the
thermoplastic polymers, and such requirement becomes severer and
severer. Especially in recent years, it is regarded as a problem
that a flame-retardant resin composition obtained by adding a
halogen-containing compound to a thermoplastic polymer or a
flame-retardant resin composition obtained by adding a
halogen-containing compound and antimony oxide to a thermoplastic
polymer, which are the mainstream of the flame retarding technique
conventionally used, generate halogenous gas when they are burned
or molded. Therefore, a flame-retardant resin composition which
generates no halogenous gas during burning or molding has been
demanded.
To meet such demand, in recent studies, there has been proposed a
method of adding, as an inorganic flame retardant, a specific
metallic hydrate which is decomposed or dehydrated by the
endothermic reaction at the combustion temperature of the resin to
inhibit combustion of the resin. In this case, however, the flame
retardance effect of the metallic hydrate is extremely low, so that
the metallic hydrate must be used in a large amount to obtain a
desired flame-retardant resin composition. As a result, the
resulting composition is reduced in the molding processability, and
besides, the molded article obtained therefrom is deteriorated in
various properties such as mechanical strength. In order to cope
with various problems caused by the use of the metallic hydrate in
a large amount, it has been proposed to further add an inorganic
compound.
For example, there are proposed the addition of molybdenum or a
molybdenum compound (Japanese Patent Laid-Open Publication No.
268738/1989) and the addition of silicon carbide whisker (Japanese
Patent Laid-Open Publication No. 9937/1991). However, even if an
inorganic compound is further added to the flame-retardant resin
composition containing metallic hydrate as a main flame retardant,
new problems caused by the use of a large amount of a flame
retardant arise, and the problems have not been fundamentally
solved yet.
Also proposed recently is a flame-retardant resin composition
obtained by adding ammonium polyphosphate in combination with one
or more nitrogen-containing organic compounds which are thermally
decomposed to generate nonflammable gas (water, carbon dioxide,
ammonia, nitrogen, etc.) and carbonaceous residue.
For example, there has been proposed a flame-retardant composition
comprising a polymer or oligomer of 1,3,5-triazine derivative and
ammonium polyphosphate (Japanese Patent Laid-Open Publication No.
147050/1984, EP-0475418). However, the flame-retardant resin
composition obtained by adding ammonium polyphosphate and the
nitrogen-containing organic compound in combination is still
insufficient in flame retardance, though it shows higher flame
retardance even in the case of using the flame retardant in a small
amount, as compared with the flame-retardant resin composition
containing metallic hydrate as the main flame retardant.
Further, Japanese Patent Laid-Open Publication No. 146452/1977
discloses a flame-retardant composition comprising ammonium
polyphosphate and a reaction product of aldehyde and a nitrogen
compound containing >C.dbd.O group, >C.dbd.S group or >NH
inserted in the ring structure; Japanese Patent Laid-Open
Publication No. 129435/1980 discloses a flame-retardant composition
comprising ammonium polyphosphate and a reaction product of
benzylguanamine and aldehyde; and Japanese Patent Laid-Open
Publication No. 53156/1979 discloses a flame-retardant composition
comprising ammonium polyphosphate and a derivative of isocyanuric
acid.
Japanese Patent Laid-Open Publication No. 14277/1989 proposes, as a
composition using flame retardants other than the
nitrogen-containing compounds, a flame-retardant composition
comprising a high-viscosity silicone oil, a silicone resin,
polyhydric alcohol and ammonium polyphosphate.
In the molded articles obtained from the conventional
flame-retardant compositions mentioned above, however, that
ammonium polyphosphate seriously bleeds out on the surface of the
molded article. This takes place under the conditions of high
temperature and high humidity such as in the wet season, though
these compositions exert a high flame retardance effect. The reason
is that the ammonium polyphosphate is hygroscopic, water-soluble
and easily hydrolyzed because of its chemical structure.
In addition, the ammonium polyphosphate more easily undergoes
hydrolysis due to the high hygroscopicity of the
nitrogen-containing compound described in the aforementioned
EP-0475418. Therefore, the molded article obtained from the
flame-retardant resin composition containing such a
nitrogen-containing compound is markedly reduced in surface
electrical resistance. As a result, such composition cannot be used
as an electrical insulating material under the conditions of high
temperature and high humidity.
Furthermore, the ammonium polyphosphate is poor in hydrolytic
stability. To improve the hydrolytic stability, research have been
conducted. Japanese Patent Publications No. 15478/1978 and No.
39930/1977 disclose a process to obtain hydrolytic-stable ammonium
polyphosphate by allowing water-insoluble melamine to react with
ammonium polyphosphate, but the resulting ammonium polyphosphate is
still insufficient in hydrolytic stability.
Japanese Patent Laid-Open Publication No. 103962/1986 discloses a
process for preparing a hydrolytic-stable finely divided
flame-resistant agent, which comprises curing ammonium
polyphosphate and a melamine-formaldehyde resin in a suspension.
However, in the course of curing the resin component in the
suspension, agglomeration of resin particles takes place thereby
making the particle diameter larger. As a result, if the finely
divided flame-resistant agent is added to thermoplastic resins,
thermosetting resins, paints, paper, etc. as one component of flame
retardants, the resulting articles are reduced in mechanical
strength.
SUMMARY OF THE INVENTION
It is a first object of the invention to provide a thermoplastic
polymer composition which shows excellent flame retardance in spite
of a low content of a flame retardant. The present inventors have
discovered a flame-retardant thermoplastic polymer composition
which exhibits excellent flame retardance even if a flame retardant
is used in a small amount, and they have found that the
aforementioned problem can be solved by adding a small amount of an
oxygen-containing solid compound containing an element of Group II,
Group III or Group IV of the periodic table to a flame-retardant
composition comprising a powder of ammonium polyphosphate (C1) or a
powder of melamine-coated ammonium polyphosphate (C2) and a
nitrogen-containing organic compound (B). The present inventors
have made further studies based on this finding and accomplished
the present invention.
It is a second object of the invention to provide a flame-retardant
polymer composition which comprises a water-insoluble ammonium
polyphosphate obtained by allowing a powder of melamine-coated
ammonium polyphosphate (C2) to react with a compound reactive to an
active hydrogen in the melamine molecule (the compound being
referred to as "crosslinking agent" hereinafter), the
nitrogen-containing organic compound (B) and the thermoplastic
polymer (D). This flame-retardant polymer composition shows such a
high bleed resistance that bleeding does not take place even in an
atmosphere of high temperature and high humidity.
The present inventors have studied to attain the second object, and
they have found that the aforementioned requirement is satisfied
with a molded article obtained from a flame-retardant polymer
composition which comprises a powder of ammonium polyphosphate
having been modified to be water-insoluble by means of the surface
crosslinking reaction (hereinafter sometimes referred to as
"water-insoluble ammonium polyphosphate of the invention"), in
place of the conventional ammonium polyphosphate powder (C1 or C2),
the nitrogen-containing compound (B) and the thermoplastic polymer
(D). As a result of further studies, the present inventors have
created a flame-retardant polymer composition which uses a
water-insoluble ammonium polyphosphate powder in place of the
component (C1) or (C2) in the above-mentioned flame-retardant
composition to attain the first object of the invention.
It is a third object of the invention to realize the first object
and the second object at the same time, and to provide a
flame-retardant polymer composition which exhibits excellent flame
retardance even if a flame retardant is used in a small amount and
which shows such a high bleed resistance so that bleeding does not
take place even in an atmosphere of high temperature and high
humidity.
In order to attain the third object, the water-insoluble ammonium
polyphosphate powder is used in place of the ammonium polyphosphate
powder (C1) in the above-mentioned flame-retardant polymer
composition to attain the first object of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an infrared spectrum of a surface of a water-insoluble
ammonium polyphosphate powder obtained in Example 28.
FIG. 2 shows an infrared spectrum of a surface of a melamine-coated
ammonium polyphosphate powder used in other examples.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention includes the following:
1. A flame-retardant thermoplastic polymer composition
comprising:
(A) an oxygen-containing solid compound containing an element
belonging to Group II, Group III or Group IV of the periodic table,
in an amount of 0.1 to 5% by weight,
(B) a nitrogen-containing organic compound in an amount of 1 to 20%
by weight,
(C) at least one powder selected from an ammonium polyphosphate
powder represented by the following formula [I], a melamine-coated
ammonium polyphosphate powder and a water-insoluble ammonium
polyphosphate powder, in an amount
(D) a thermoplastic polymer in an amount of 88.9 to 35% by
weight,
the total amount of said components (A), (B), (C) and (D) being
100% by weight; ##STR1## wherein n is a number of not less than 2.
2. The flame-retardant thermoplastic polymer composition as
described in the above item 1, wherein the element belonging to
Group II, Group III or Group IV of the periodic table is at least
one element selected from Ca, Ba, Sr, Mg, Al, Si, Zn, Cd, Ti, Zr
and Sn.
3. The flame-retardant thermoplastic polymer composition as
described in the above item 1 or 2, wherein the oxygen-containing
solid compound is at least one compound selected from hydroxides,
basic carbonates, carbonates, carbonate hydrates, silicates,
silicate hydrates, oxides, oxide hydrates and complexes composed of
two or more kinds thereof.
4. The flame-retardant thermoplastic polymer composition as
described in any one of the above items 1 to 3, wherein the
oxygen-containing solid compound has a mean particle diameter of
not more than 10 .mu.m.
5. The flame-retardant thermoplastic polymer composition as
described in any one of the above items 1 to 4, wherein the
nitrogen-containing organic compound is a homopolymer and/or a
copolymer, each comprising constituent units represented by the
following formula [II]: ##STR2## wherein X and Z.sup.1 are each a
group bonded to a triazine skeleton through a nitrogen atom; X is
an alkylamino group represented by --NHR.sup.1 or --NR.sup.2
R.sup.3, said R.sup.1, R.sup.2 and R.sup.3 each being a linear or
branched alkyl group having 1 to 6 carbon atoms (R.sup.2 and
R.sup.3 may be different from each other), a morpholino group, a
piperidino group or a hydroxyalkylamino group represented by
--NHR.sup.4 or --NR.sup.5 R.sup.6, said R.sup.4, R.sup.5 and
R.sup.6 each being a linear or branched hydroxyalkyl group having 2
to 6 carbon atoms (R.sup.5 and R.sup.6 may be different from each
other); and Z.sup.1 is a divalent group of piperazine, a divalent
group represented by --HN(CH.sub.2).sub.m NH-- (m is a number of 2
to 6) or a group represented by --NR.sup.7 (CH.sub.2).sub.n R.sup.8
N-- (n is a number of 2 to 6), R.sup.7 and R.sup.8 being a linear
or branched alkyl group having 1 to 6 carbon atoms or a
hydroxyethyl group and at least one of said R.sup.7 and R.sup.8
being a hydroxyethyl group.
6. The flame-retardant thermoplastic polymer composition as
described in any one of the above items 1 to 5, wherein the
nitrogen-containing organic compound is a product obtained by the
reaction of cyanuric chloride with diamine.
7. The flame-retardant thermoplastic polymer composition as
described in any one of the above items 1 to 6, wherein the
thermoplastic polymer is at least one polymer selected from olefin
resins, styrene resins and thermoplastic elastomers.
8. Flame-retardant thermoplastic polymer compositions
comprising:
(C) a water-insoluble ammonium polyphosphate powder in an amount of
10 to 40% by weight, said powder being obtained by coating surfaces
of ammonium polyphosphate particles with a crosslinked structure
formed by the reaction of an active hydrogen with compounds having
a functional group reactive to the active hydrogen, said active
hydrogen serving to form an amino group of a melamine molecule
present within a coated layer of particles of melamine-coated
ammonium polyphosphate (C2),
(B) nitrogen-containing organic compounds in amounts of 1 to 20% by
weight, and
(D) thermoplastic polymers in amounts of 89 to 40% by weight,
the total amount of said components (C), (B) and (D) being 100% by
weight.
9. The flame-retardant thermoplastic polymer compositions as
described in the above item 8, wherein the compounds having a
functional group reactive to active hydrogen for forming an amino
group of a melamine molecule are organic compounds containing at
least one group selected from an isocyanate group, a glycidyl
group, a carboxyl group, a methylol group and an aldehyde
group.
10. The flame-retardant thermoplastic polymer compositions as
described in the above item 8 or 9, wherein the melamine-coated
ammonium polyphosphate is melamine-coated ammonium polyphosphate
obtained by coating an ammonium polyphosphate powder with melamine
in an amount of 0.5 to 20% by weight.
11. The flame-retardant thermoplastic polymer compositions as
described in any one of the above items 8 to 10, wherein the
nitrogen-containing organic compounds are homopolymers having one
monomer represented by the following formula [II] as a constituent
unit and/or copolymers of two or more kinds of said monomers;
##STR3## wherein each of X and Z.sup.1 has a structure bonded to a
triazine ring through a nitrogen atom; X is an alkylamino group
represented by --NHR.sup.1 or --NR.sup.2 R.sup.3, said R.sup.1,
R.sup.2 and R.sup.3 each being a linear or branched alkyl group
having 1 to 6 carbon atoms (R.sup.2 and R.sup.3 may be different
from each other), a morpholino group, a piperidino group or a
hydroxyalkylamino group represented by at least one of --NHR.sup.4
and --NR.sup.5 R.sup.6 (R.sup.5 and R.sup.6 may be different from
each other); and Z.sup.1 is a piperazinylene group, a group
represented by --NH(CH.sub.2).sub.m NH-- (m is a number of 2 to 6)
or a group represented by --NR.sup.7 (CH.sub.2).sub.n R.sup.8 N--
(R.sup.7 and R.sup.8 may be different from each other and n is a
number of 2 to 6) and R.sup.4, R.sup.5, R.sup.6, R.sup.7 and
R.sup.8 are as defined above.
12. The flame-retardant thermoplastic polymer compositions as
described in any one of the above items 8 to 11, wherein the
nitrogen-containing organic compounds (B) are products obtained by
the reaction of cyanuric chloride with diamines.
13. The flame-retardant thermoplastic polymer compositions as
described in any one of the above items 8 to 12, wherein the
thermoplastic polymers (D) are aliphatic thermoplastic resins,
aromatic thermoplastic resins, aliphatic elastomers, aromatic
elastomers, mixtures of two or more kinds of said elastomers, or
thermoplastic elastomers known as mixtures of thermoplastic resins
and elastomers or partial-crosslinked elastomers.
14. The flame-retardant thermoplastic polymer compositions as
described in any one of the above items 8 to 13, wherein the
thermoplastic polymers (D) are thermoplastic resins or mixtures of
two or more kinds of thermoplastic resins selected from the
following homopolymers and copolymers:
(1) .alpha.-olefin homopolymer resins or .alpha.-olefin copolymer
resins,
(2) polymer resins of vinyl monomers or their derivatives,
(3) one kind of a resin or mixtures of two or more kinds of resins
selected from nylons (polyamide resins),
(4) one kind of a thermoplastic resin or mixtures of two or more
kinds of thermoplastic resins selected from homopolymer resins of
aromatic compounds or copolymer resins of aromatic compounds,
(5) one kind of a thermoplastic elastomer or compositions of two or
more kinds of thermoplastic elastomers, and
(6) one kind of an elastomer or mixtures of two or more kinds of
elastomers selected from addition polymerization type elastomers or
condensation polymerization type elastomers.
15. The flame-retardant thermoplastic polymer compositions as
described in any one of the above items 8 to 14, wherein the
thermoplastic polymer is at least one polymer selected from the
following polymers:
ethylene resins, propylene resins, 1-butene resins and
4-methyl-1-pentene resins, which belong to the group (1);
styrene resins, styrene-.alpha.-methylstyrene resins,
poly(meth)acrylic acid resins, poly(meth)acrylic acid derivative
resins, polyvinyl chloride resins, polyvinylidene chloride resins
and acrylonitrile-butadiene-styrene type monomer copolymer resins,
which belong to the group (2);
6-nylons, 7-nylons, 6,6-nylons, 6,7-nylons, 6,10-nylons,
6,12-nylons, 6-/-6,6-copolycondensation nylons and
m-xylylene-adipic acid type nylons, which belong to the group
(3);
polycarbonate resins, polyethylene terephthalate resins,
polybutylene terephthalate resins, polysulfone resins, polyurethane
resins and polyphenylene ether resins, which belong to the group
(4);
mixtures of ethylene-propylene copolymer elastomers and ethylene
resins, mixtures of ethylene-propylene copolymer elastomers and
propylene resins, mixtures of ethylene-propylene copolymer
elastomers and ethylene resins wherein the elastomer component is a
partial-crosslinked product, and mixtures of ethylene-propylene
copolymer elastomers and propylene resins wherein the elastomer
component is a partial-crosslinked product, which belong to the
group (5); and
ethylene-propylene copolymer elastomers, ethylene-1-butene
copolymer elastomers, propylene-1-butene copolymer elastomers,
natural rubbers, polybutadiene rubbers, polyisoprene rubbers,
isobutene-isoprene copolymer rubbers, butadiene-acrylonitrile
copolymer rubbers and chloroprene rubbers, which belong to the
group (6).
16. A water-insoluble ammonium polyphosphate powder obtained by
bonding melamine molecules present on surfaces of melamine-coated
ammonium polyphosphate particles to a crosslinking agent having a
functional group reactive to active hydrogen for forming the
melamine molecules so as to crosslink the surface of the
melamine-coated ammonium polyphosphate powder.
17. The water-insoluble ammonium polyphosphate powder as described
in the above item 16, wherein the mean particle diameter of the
water-insoluble ammonium polyphosphate powder is not more than 50
.mu.m.
18. A process for preparing a water-insoluble ammonium
polyphosphate powder, comprising the steps of coating a surface of
melamine-coated ammonium polyphosphate powder with a crosslinking
agent having a functional group reactive to an active hydrogen for
forming an amino group of a melamine molecule by means of
attachment or impregnation and allowing the melamine molecule to
react with the crosslinking agent.
19. The process for preparing a water-insoluble ammonium
polyphosphate powder as described in the above item 18, wherein a
crosslinking agent having at least one group selected from the
group consisting of an isocyanate group, an oxymethyl group, a
formyl group and an epoxy group as the functional group reactive to
an active hydrogen for forming an amino group of the melamine
molecule is used.
Preferred Embodiments of the Invention
Oxygen-containing solid compound (A):
The oxygen-containing solid compound (A) (component (A)) containing
an element belonging to Group II, Group III or Group IV of the
periodic, which constitutes the flame-retardant composition of the
invention, is a compound which improves the flame retardance when
added in a small amount to a composition comprising a thermoplastic
polymer (component (D), serving as a substrate), an ammonium
polyphosphate powder, a melamine-coated ammonium polyphosphate
powder or a water-insoluble ammonium polyphosphate powder
(component (C)) and a nitrogen-containing organic compound
(component (B)).
The above-mentioned element is at least one element selected from
Ca, Ba, Sr, Mg, Al, Si, Zn, Cd, Ti, Zr and Sn. The
oxygen-containing solid compound is at least one compound selected
from hydroxides, basic carbonates, carbonates, carbonate hydrates,
silicates, silicate hydrates, oxides and oxide hydrates of the
above elements, and complexes of two or more kinds thereof.
Particular examples of such compounds include calcium hydroxide,
barium hydroxide, magnesium hydroxide, basic magnesium carbonate,
basic zinc carbonate, calcium silicate hydrate, magnesium oxide
hydrate, aluminum hydroxide, aluminum oxide hydrate, titanium oxide
hydrate, hydrotalcite (Mg.sub.6 Al.sub.2 (OH).sub.16
CO.sub.3.4H.sub.2 O), kaolinite (Al.sub.2
O.sub.3.2SiO.sub.2.2H.sub.2 O), sericite (K.sub.2 O.3Al.sub.2
O.sub.3.6SiO.sub.2.2H.sub.2 O), pirophylite (Al.sub.2
O.sub.3.4SiO.sub.2.H.sub.2 O), bentonite (Al.sub.2
O.sub.3.4SiO.sub.2.2H.sub.2 O) and talc (3MgO.4SiO.sub.2.H.sub.2
O).
The oxygen-containing solid compound (component (A)) for forming
the flame-retardant composition of the invention is particulate,
and the mean particle diameter thereof is preferably not less than
10 .mu.m. The amount of the component (A) to be added is in the
range of usually 0.1 to 5% by weight, preferably 0.5 to 2% by
weight, based on the amount of the resulting composition. When the
amount thereof is not more than 0.05% by weight, the flame
retardance is not sufficiently improved. When the amount thereof is
not less than 7% by weight, the flame retardance imparting effect
is markedly reduced.
Nitrogen-containing organic compound (B) and preparation of the
same:
The nitrogen-containing organic compound (B) (component (B)) for
forming the flame-retardant composition of the invention is an
organic compound which is thermally decomposed by ignition or
contact with flame to generate nonflammable gas (water, carbon
dioxide, ammonia, nitrogen, etc.) and carbonaceous residue when it
is present together with the ammonium polyphosphate powder, the
melamine-coated ammonium polyphosphate powder or the
water-insoluble ammonium polyphosphate powder (component (C)) in
the thermoplastic polymer (component (D)). The component (B) is a
homopolymer and/or a copolymer, each comprising constituent units
represented by the aforesaid formula [II]. The constituent units
are exemplified by the following compounds [1] and [2]:
[1] 2-piperazinylene-4-morpholino-1,3,5-triazine,
2-piperazinylene-4-piperidino-1,3,5-triazine,
2-piperazinylene-4,N,N-bis(2-hydroxylethyl)amino-1,3,5-triazine,
2-piperazinylene-4-N-(2-hydroxyethyl)amino-1,3,5-triazine: and
[2] products obtained by the reaction of cyanuric chloride with
diamines.
Examples of the above products [2] include:
(i) products obtained by the reaction of cyanuric chloride with
diamines preferably in a molar ratio of 2/3 (cyanuric
chloride/diamine),
(ii) products obtained by the reaction of cyanuric chloride with
ethylenediamine in a molar ratio of 2/3 (cyanuric
chloride/ethylenediamine), and
(iii) products obtained by the reaction of cyanuric chloride with
1,3-diaminopropane in a molar ratio of 2/3 (cyanuric
chloride/1,3-diaminopropane).
Conventionally known nitrogen-containing organic compounds may be
employed in combination with the above-mentioned
nitrogen-containing organic compound (B). For example, there can be
employed a reaction product of aldehyde with a heterocyclic
nitrogen compound containing at least one group of >C.dbd.O,
>C.dbd.S and >NH inserted in the cyclic structure, a reaction
product of benzylguanamine with aldehyde, and isocyanuric acid
derivatives such as tris(2-hydroxyethyl)isocyanurate,
tris(3-hydroxy-N-propyl) isocyanurate and
tris(2,3-epoxypropyl)isocyanurate.
Homopolymerization of triazine type monomer:
A homopolymer having 2-piperazinylene-4-morpholino-1,3,5-triazine
(i.e., the aforesaid formula [II]) as its constituent unit, that is
an example of the nitrogen-containing organic compound (B), can be
obtained by, for example, the following process.
2,6-Dihalo-4-morpholino-1,3,5-triazine (e.g.,
2,6-dichloro-4-morpholino-1,3,5-triazine or
2,6-dibromo-4-morpholino-1,3,5-triazine) and piperazine are reacted
with each other in an equimolar ratio with heating in an inert
solvent such as xylene in the presence of an organic or inorganic
base (e.g., triethylamine, tributylamine, sodium hydroxide,
potassium hydroxide or sodium carbonate). After the reaction is
completed, the reaction product is filtered to collect a solid. The
solid is washed with boiling water to remove a salt (by-product)
and dried.
The resulting homopolymer having
2-piperazinylene-4-morpholino-1,3,5-triazine as its constituent
unit is insoluble in ordinary organic solvents, and the melting
point thereof is unmeasurable. This homopolymer has a decomposition
temperature of about 304.degree. C. and a true density of 1.3
g/cc.
A homopolymer having
2-piperazinylene-4-bis(2-hydroxyethyl)amino-1,3,5-triazine as its
constituent unit can be obtained in a manner similar to that
described above using
2,6-dihalo-4-bis(2-hydroxyethyl)amino-1,3,5-triazine as a starting
material.
A copolymer having 2-piperazinylene-4-morpholino-1,3,5-triazine and
2-piperazinylene-4-bis(2-hydroxyethyl)amino-1,3,5-triazine as its
constituent units can be obtained in a manner similar to that
described above using a mixture of
2,6-dihalo-4-morpholino-1,3,5-triazine and
2,6-dihalo-4-bis(2-hydroxyethyl)amino-1,3,5-triazine as a starting
material. A mixing ratio between
2,6-dihalo-4-morpholino-1,3,5-triazine and
2,6-dihalo-4-bis(2-hydroxyethyl)amino-1,3,5-triazine can be
arbitrarily selected to obtain a copolymer having an arbitrary
monomer ratio.
For obtaining a reaction product of cyanuric chloride with
ethylenediamine, cyanuric chloride and ethylenediamine are reacted
with each other in a molar ratio of 2/3 (the former/the latter) in
the presence of an organic or inorganic base (e.g., triethylamine,
tributylamine, sodium hydroxide, potassium carbonate or sodium
carbonate) using water as a solvent. The reaction is initiated at a
temperature of not higher than 10.degree. C. and carried out with
slowly heating the system up to the reflux temperature of the
solvent. After the reaction is completed, the reaction product is
filtered to collect a solid. The solid is washed with boiling water
to remove a salt (by-product), and the remaining solid is dried.
The solid reaction product thus obtained is insoluble in organic
solvents, and the solubility thereof in water at room temperature
is not more than 0.1%. The decomposition temperature thereof is
324.degree. C.
Amount of nitrogen-containing compound (B):
The amount of the component (B) to be added is in the range of
usually 1 to 20% by weight, preferably 3 to 18% by weight, based on
the weight of the resulting composition. When the amount thereof is
not more than 0.5% by weight, the flame retardance is not
sufficiently improved. On the other hand, even if the amount
thereof is not less than 25% weight, further improvement in the
flame retardance cannot be expected.
REFERENCE EXAMPLE 1
Ammonium polyphosphate powder (C1) and preparation of the same:
The powder of ammonium polyphosphate (C1) (component (C)) used in
the invention is represented by the aforesaid formula [I]. The
powder of melamine-coated ammonium polyphosphate (C2) is that
obtained by coating the surface of the ammonium polyphosphate
powder (C1) represented by the formula [I] with melamine molecules
by means of chemical "addition" or physical "adsorption". The
powder of water-insoluble ammonium polyphosphate (C3-C5) is that
obtained by allowing active nitrogen which forms amine of melamine
in the melamine coat of the melamine-coated ammonium polyphosphate
(C2) to react with a crosslinking agent having a functional group
reactive to the active nitrogen.
The term "addition" used herein means that the melamine molecule is
linked to a proton of an oxygen-proton bond derived from ammonium
polyphosphate (C1) by means of ions. The melamine molecule in this
state is stable even when heated, and is hardly released again. The
term "adsorption" means that the melamine molecule is physically
adsorbed on the surface of the ammonium polyphosphate powder (C1).
The melamine molecule in this state repeatedly undergoes
sublimation from the surface of the ammonium polyphosphate powder
(C1) and adsorption thereon repeatedly occurs when continuously
heated, so as to be chemically linked to the proton of the
oxygen-proton bond. The amount of the melamine molecules used
herein is in the range of 0.5 to 20% by weight, preferably 2 to 10%
by weight, based on the amount of the ammonium polyphosphate (C1).
All the melamine molecules used are added or adsorbed on the
surface of the ammonium polyphosphate powder (C1) to obtain a
powder of melamine-coated ammonium polyphosphate (C2).
First step
Into a heating-kneading device such as a preheated kneader, a
powder of ammonium polyphosphate (C1) represented by the aforesaid
formula [I] is introduced in a given amount and heated for 0.5 to 5
hours at such a temperature that the ammonium polyphosphate powder
is not melted and ammonia is easily eliminated from the ammonium
polyphosphate, i.e., not higher than 300.degree. C., preferably
200.degree. to 300.degree. C. As a result, ammonia, which is
present inherently in a stoichiometric quantity in the ammonium
polyphosphate (C2), is eliminated in part (about 5 to 10% by weight
based on the stoichiometric quantity of ammonia).
Through the above process, there is produced ammonium polyphosphate
lacking of a part ammonia or ammonium polyphosphate in which
ammonia is bonded in the quantity of not more than the
stoichiometric quantity in the process for preparing conventional
ammonium polyphosphate (both sometimes referred to as
"ammonia-short ammonium polyphosphate" hereinafter) in the form of
a suspension (concentration: 1% by weight, pH: 4.0 to 6.0) or a
powder.
Second step:
In the same device as described above, the "ammonia-short ammonium
polyphosphate" powder is heated at a temperature of 250.degree. to
300.degree. C. (i.e., temperature at which the ammonium
polyphosphate is not melted and the melamine molecules used for
coating can be sublimated), and the melamine molecules are added
thereto. As a result, ammonia is eliminated from the surface of the
"ammonia-short ammonium polyphosphate" powder to alter the ammonium
polyphosphate to polyphosphoric acid, and the melamine molecules
are bonded to the oxygen-proton bond of the polyphosphoric
acid.
As the ammonium polyphosphate, that is a starting material of the
component (C) used in the invention, i.e., the ammonium
polyphosphate powder (C1), the melamine-coated ammonium
polyphosphate powder (C2) or the water-insoluble ammonium
polyphosphate, commercially available ones can be employed.
Examples of the commercially available ones include SUMISAEE-P
(trade name, available from Sumitomo Chemical Co., Ltd.),
EXOLIT-422 (trade name, available from Hoechst Co.), EXOLIT-700
(trade name, available from Hoechst Co.) and PHOSCHECK P/40 (trade
name, available from Monsanto Co.). Also employable is a powder of
ammonium polyphosphate (crystal form II) (C6) described in Japanese
Patent Laid-Open Publication No. 300204/1992. The powder of
ammonium polyphosphate (crystal form II) (C6) can be obtained, for
example, by the process described later.
Amount of ammonium polyphosphate powder (C):
The amount of the ammonium polyphosphate powder (C1 or C6) or the
melamine-coated ammonium polyphosphate powder (C2) to be added to
the thermoplastic polymers (D) is usually in the range of 10 to 40%
by weight, preferably 15 to 26% by weight, based on the amount of
the resulting composition. When the amount thereof is not more than
7% by weight, particularly not more than 5% by weight, the flame
retardance is not sufficiently improved. On the other hand, even if
the amount thereof is not less than 50% weight, particularly not
less than 45% by weight, further improvement in the flame
retardance cannot be expected. The same can be said with the
water-insoluble ammonium polyphosphate (C3-C5).
REFERENCE EXAMPLE 2
Preparation of ammonium polyphosphate (crystal form II) (C6)
The ammonium polyphosphate (crystal form (II)) (C6) used is
prepared in the following manner.
A mixture of 660 g (5 mol) of diammonium hydrogen phosphate and 710
g (5 mol) of phosphorus pentoxide was introduced into a 5-liter
bench kneader preheated to 290.degree. to 300.degree. C. in a
nitrogen atmosphere and was stirred for 20 minutes with heating of
the kneader. Then, to the mixture was added 195 g of an urea
solution (concentration: 76.9%) of 80.degree. C. by means of
spraying. Subsequently, the resulting mixture was heated at
250.degree. to 270.degree. C. for 2.5 hours in an ammonia
atmosphere to obtain 1,460 g of an ammonium polyphosphate
powder.
This ammonium polyphosphate powder was a mixture of individual
particles and agglomerates thereof. In order to process the
agglomerates into individual particles, the agglomerates were
pulverized in an ammonia atmosphere using a pulverizer [trade name:
HOSOKAWAMICRON AP-B type, produced by Hosokawa Micron K.K.]. The
X-ray diffraction pattern of the ammonium polyphosphate powder
obtained was analyzed. As a result, it was confirmed that the type
of the crystal thereof was type II, that is, the obtained product
was ammonium polyphosphate (crystal form II) (C6), and the mean
particle diameter thereof was 6.4 .mu.m.
As the melamine molecules used for preparing the melamine-coated
ammonium polyphosphate powder (C2), those commercially available as
"melamine monomers" can be employed.
Preparation of water-insoluble ammonium polyphosphate (C3-C5):
The powder of water-insoluble ammonium polyphosphate (C3-C5), that
is a main flame retardant used for preparing the secondary
flame-retardant composition to attain the second object of the
invention, is an ammonium polyphosphate powder having been surface
crosslinked in the following manner.
The melamine molecules are added and/or adsorbed on the surface of
the powder of ammonium polyphosphate (C1 or C6) by sublimation of
the melamine molecules, to initially prepare a powder of
melamine-coated ammonium polyphosphate (C2). Then, the melamine
molecules present on the surface coat of each particle of the
powder (C2) are allowed to react with a specific compound so as to
form a crosslinked structure on the surface of the powder (C2),
whereby the powder is modified to water-insoluble. This
crosslinking reaction is a reaction of an active hydrogen which
forms an amino group of the melamine molecule with a functional
group which is contained in the specific compound and reactive to
the active hydrogen.
Into a reactor equipped with a heating-stirring means or a
heating-kneading means, the melamine-coated ammonium polyphosphate
and a compound having a functional group reactive to an active
hydrogen which forms an amino group of the melamine molecule, e.g.,
a formaldehyde aqueous solution, are introduced, and they are
mixed. Then, the reactor is heated to a temperature at which a
crosslinked structure can be easily formed among the active
hydrogens which form amino groups of the melamine molecules,
usually 80.degree. to 200.degree. C., preferably 100.degree. to
150.degree. C., for 0.5 to 2 hours, thereby to obtain a
water-insoluble ammonium polyphosphate powder of the invention in
which a crosslinked structure is formed in the melamine coat of the
melamine-coated ammonium polyphosphate.
In the crosslinking reaction mentioned above, a single crosslinking
agent is used. Therefore, the crosslinking reaction between the
active hydrogen forming the amino group of the melamine molecule
and the crosslinking agent on the same particle of the
melamine-coated ammonium polyphosphate is carried out carefully, so
that minimal crosslinking among the different particles by the
cross linking agent takes place. Accordingly, the reaction proceeds
in any of a solvent system and a non-solvent system. As the solvent
system, any of a single solvent system and a mixed solvent system,
i.e., water and/or organic solvents, can be employed.
The crosslinking agent used is a compound having one or more
functional groups reactive with active hydrogen which forms an
amino group of the melamine molecule, and the amount of the
crosslinking agent is 0.5 to 6 mol equivalent times, preferably 1
to 2 mol equivalent times, in terms of the functional group
contained therein, based on the melamine molecules contained in the
melamine-coated ammonium polyphosphate. If the amount thereof is
smaller than 0.5 mol equivalent times, a crosslinked structure is
not sufficiently formed in the melamine coat, and therefore
improvement in hydrolytic stability cannot be expected. On the
other hand, if the amount thereof is larger than 6 mol equivalent
times, there arises the unfavorable result of residual unreacted
crosslinking agent.
Examples of the functional groups reactive with the active hydrogen
which forms the amino group of the melamine molecule include an
isocyanate group, an oxymethyl group, a formyl group and an epoxy
group. Examples of the compounds having one or more isocyanate
groups include 1,6-diisocyanatehexane,
1,1-dimethylenebis(4-isocyanatebenzene),
3,3'-dimethyldiphenyl-4,4'-diisocyanate and
1,5-diisocyanonaphthalate. Examples of the compounds having one or
more methylol groups include methylolurea, methylol melamine,
trimethylolethane and trimethylolpropane. Examples of the compounds
having one or more aldehyde groups include formaldehyde, malonic
aldehyde and glyoxal. Examples of the compounds having one or more
epoxy groups include ethylene glycol diglycidyl ether, glycerol
polyglycidyl ether and various epoxy resins such as bisphenol A
type epoxy resins, phenolic novolak type epoxy resins and alicyclic
epoxy resins. These compounds are all commercially available.
Thermoplastic polymers (D):
The thermoplastic polymer (D) (component (D)), which serves as a
substrate of the flame-retardant composition of the invention, is
at least one polymer selected from high-crystalline polymers,
low-crystalline polymers, amorphous polymers and
partial-crosslinked polymers. In other words, the thermoplastic
polymer (D) used in the invention includes all substances capable
of being molded by ordinary resin molding methods, and the meaning
of the term "thermoplastic polymer" is not limited to "resins" but
may include wax-like substances, elastomer-like substances and
thermoplastic elastomers having both resin properties and the
elastomeric properties.
Accordingly, substances whose melting points (Tm) are unmeasurable
but whose softening points (Sp) are measurable and substances
having indefinite melting points, such as a glass-like polymer
called a "solid solution", are all included in the thermoplastic
polymer (D) used as a substrate of the invention.
Listed below are preferred examples of the thermoplastic polymers
(D) employable in the invention.
(1) 1-Olefin (.alpha.-olefin) resins:
one kind of a resin and mixtures (resin blends) of two or more
kinds of resins selected from polyethylene resins, polypropylene
resins, poly-1-butene resins, poly-4-methyl-1-pentene resins,
poly-1-hexene resins, poly-1-octene resins and poly-1-decene
resins
Of the above polyolefin resins, preferred are crystalline
polypropylene resins, particularly, a propylene homopolymer
crystalline resin and copolymer crystalline resins of propylene and
ethylene or propylene and at least one 1-olefin having 4 or more
carbon atoms. Examples of the 1-olefins having 4 or more carbon
atoms include 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene,
1-octene and 1-decene. Of the above resins, most useful are
propylene-ethylene copolymer crystalline resins and
propylene-1-butene copolymer crystalline resins.
Also preferred are ethylene polymers. Examples of the ethylene
polymers include a crystalline ethylene homopolymer and crystalline
copolymers of ethylene and 1-olefins having 3 or more carbon
atoms.
(2) Styrene resins:
polystyrene resins (PS), high-impact polystyrene resins (HIPS),
heat-resistant polystyrene resins (including
styrene-.alpha.-methylstyrene copolymer resin),
acrylonitrile-styrene copolymer resins (AS) and
acrylonitrile-butadiene-styrene copolymer resins (ABS)
Also employable are the following crystalline or amorphous
thermoplastic resins.
(3) Vinyl resins:
polyvinyl chloride resin (PVC), polyvinylidene chloride resin
(PVDC), polymethyl acrylate resin (PMA) and polymethyl methacrylate
resin (PMMA)
(4) One kind of a nylon (polyamide resin) or mixtures of two or
more kinds of nylons:
6-nylon, 7-nylon, 11-nylon, 12-nylon, 6,6-nylon, 6,10-nylon,
6,12-nylon, and all aromatic nylons, e.g., condensate of
terephthalic acid unit and p-phenylenediamine unit,
m-xylylene-adipic acid condensation nylons (MXD6),
6-/6,6-copolycondensation nylon and 6-/12-copolycondensation
nylon
(5) Thermoplastic polyester resins:
polyethylene terephthalate, polybutylene terephthalate, and all
aromatic polyesters, e.g., polyphenylene terephthalate. (linking a
hydroquinone unit and terephthalic acid unit).
(6) One kind of a thermoplastic resin or mixtures of two or more
kinds of thermoplastic resins selected from homopolymer resins of
aromatic compounds and copolymer (including cocondensate) resins of
aromatic compounds:
polycarbonate resins (PC), polysulfone resins, polyphenylene ether
resins (PPE), acrylonitrile-styrene-1,3-butadiene copolymer resins
(ABS) and polyurethane resins (PU)
Elastomers:
The thermoplastic polymers (D) for forming the flame-retardant
thermoplastic polymer composition of the invention further include
resin blends containing small amounts of elastomers, and
"thermoplastic elastomers". The thermoplastic elastomers include
not only simple blends (compositions) composed of resins and
elastomers but also other compositions in which elastomers are
contained in the partial-crosslinked form. For obtaining these
compositions, the resin components and the elastomer components
must be kneaded at a temperature not lower than the highest
softening point of those components. Examples of the elastomers are
described below.
(7) One kind of an elastomer or mixtures of two or more kinds of
elastomers selected from the following addition polymerization type
elastomers and condensation polymerization type elastomers:
(i) One kind of an elastomer or mixtures of two or more kinds of
elastomers selected from .alpha.-olefin copolymer elastomers
ethylene-propylene copolymer elastomers (EPM) and
ethylene-propylene-nonconjugated diene copolymer elastomers (EPDM),
particularly, ethylene-propylene-2-ethylidene-5-norbornene
copolymer elastomers (EPDM) and propylene-1-butene copolymer
elastomers (PBM)
(ii) One kind of a rubber or mixtures of two or more kinds of
rubbers selected from homopolymer rubbers of nonconjugated dienes
and copolymer rubbers of nonconjugated dienes
poly-1,3-butadiene rubber (BR), polyisoprene rubber (IR),
acrylonitrile-1,3-butadiene copolymer rubber (NBR), chloroprene
rubbers, isobutene-isoprene rubbers (IIR, commonly called "butyl
rubber") and natural rubbers (NR)
The above-mentioned various elastomers are conceptually classified
into the following groups.
Polyolefin elastomers (D3), e.g., an ethylene-propylene copolymer
elastomer (EPM), an ethylene-propylene-nonconjugated diene
copolymer elastomer (EPDM), a partial-crosslinked product of a
composition composed of an ethylene crystalline polymer and an
ethylene-propylene-nonconjugated diene copolymer elastomer, and a
partial-crosslinked product of a composition composed of a
propylene crystalline polymer and an
ethylene-propylene-nonconjugated diene copolymer elastomer
(8) Elastomers obtained by condensation polymerization:
polyurethane elastomers
Other additives:
The flame-retardant thermoplastic polymer composition of the
invention may contain various additives which are generally added
to thermoplastic polymers, for example, antioxidant (particularly,
steric hindrance phenol type stabilizer), heat stabilizer,
ultraviolet inhibitor, antistatic agent, copper harm inhibitor,
lubricant, neutralizing agent, nucleating agent and pigment.
Examples of the neutralizing agents include metallic salts of
higher fatty acids and complex salts of metallic oxides or metallic
hydroxides, such as hydrotalcite, manaseite, talc, mica and white
carbon.
Other than the above additives, high-viscosity silicone oil,
silicone resins and polyhydric alcohols may be also added. Instead
of the polyhydric alcohols, IIA Group metal salts of higher
aliphatic carboxylic acids (E3), such as magnesium stearate and
calcium stearate, may be used.
The high-viscosity silicone oil is dialkylpolysiloxane which is
substantially linear. Useful examples thereof are polymers of
dimethylsiloxane having a viscosity of about 90,000 to 150,000 cps
at 25 .degree. C. The silicone resins are MQ silicone resins
generally formed from monofunctional "M units" having an average
composition formula (R.sup.9).sub.3 SiO.sub.0.5 (wherein R.sup.9 is
a saturated or an unsaturated hydrocarbon group such as alkyl,
aryl, vinyl or allyl group) and four-functional "Q units" having an
average composition formula SiO.sub.2, and having a ratio of the "M
units" to the "Q units" (M/Q) of 0.3 to 0.4.
Examples of the polyhydric alcohols include pentaerythritols such
as pentaerythritol, dipentaerythritol and tripentaerythritol.
The high-viscosity silicone oil, silicone resins and polyhydric
alcohols which may be added to the composition of the invention as
additives (E) are not limited to those of special qualities, and
satisfactory effects can be exerted by the use of commercially
available ones.
Preparation of the polymer composition of the primary flame
retardance formulation according to the invention:
The thermoplastic polymer composition of the primary flame
retardance formulation according to the invention can be prepared
by, for example, the following process. The thermoplastic polymer
(D) (serving as a substrate), the oxygen-containing solid compound
(A), the ammonium polyphosphate (C1 or C6) or the melamine-coated
ammonium polyphosphate (C2), the nitrogen-containing organic
compound (B), and if necessary, other additives (E) are introduced
in given amounts into an appropriate mixing apparatus such as
Henschel mixer (trade name), super mixer or tumbling mixer, and
they are stirred and mixed for 1 to 10 minutes. The resulting
mixture is melt kneaded at a temperature of 170.degree. to
220.degree. C. and extruded into strands by means of a roll mill or
a screw extruder (or a vented extruder, if necessary). The strands
are then cut and pelletized to obtain the aimed flame-retardant
composition.
EXAMPLES
The present invention will be further described with reference to
the following examples, but it should be construed that the
invention is in no way limited to those examples.
In the following examples, flame retardance and other properties
were evaluated in the manner described below.
(1) Flame retardance: UL94V
The flame retardance was evaluated in accordance with the vertical
burning test defined in "Burning Test of Plastic Materials for
Machine Parts" of UL Subject 94 (Underwriter Laboratories
Inc.).
thickness of specimen (primary flame retardance formulation): 1.2
mm (1/21 inch),
thickness of specimen (secondary flame retardance formulation): 1.6
mm (1/16 inch)
(2) Flame retardance: oxygen index (O.I.)
The flame retardance was also evaluated by measuring the oxygen
index in accordance with JIS (Japanese Industrial Standard) K7201
(burning test of polymer materials by the oxygen index method).
(3) Evaluation of hydrolytic stability
A water-soluble component contained in the product was
quantitatively determined. For the quantitative determination of
the water-soluble component, 1 g of the ammonium polyphosphate
powder obtained was suspended in 99 g of pure water to prepare
three samples of 1 wt. % suspension. These samples were stirred for
1 hour at 25.degree. C., 50.degree. C. and 75.degree. C.,
respectively, and then subjected to centrifugal separation. The
supernatant liquid was filtered through a filter paper (thickness:
0.45 .mu.m). A given amount of the filtrate was placed in a
laboratory dish and evaporated to dryness in a dryer. From the
amount of the residue, the amount of the water-soluble component
was calculated to evaluate the hydrolytic stability. The smaller
the value of the amount of the water-soluble component is, the
higher the hydrolytic stability is.
(4) Measurement of mean particle diameter
A powder to be measured was dispersed in an ethyl alcohol
dispersing medium, and the mean particle diameter of the powder was
measured using a laser diffraction/scattering type particle size
distribution measuring device (trade name: LA-700, produced by
Horiba Seisakusho K.K.).
(5) Measurement of mechanical strength
Into Cooking Mixer (trade name) were introduced 70% by weight of a
propylene-ethylene crystalline copolymer [ethylene content: 8.0% by
weight, MFR (230.degree. C., 2.16 kgf): 20 g/10 min] as a
polypropylene resin (D), 20% by weight of water-insoluble ammonium
polyphosphate (C) obtained in each example, 10% by weight of a
2-piperazinylene-4-morpholino-1,3,5-triazine polymer (B), and 0.15%
by weight of 2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl thiodipropionate (E2) and 0.1% by weight of calcium
stearate (E3), each as an additive (E), and they were mixed for 1
hour.
The resulting mixture was kneaded and extruded using CSI-Max Mixing
Extruder (Model CS-194A, trade name) to prepare pellets. The
pellets of the flame-retardant resin composition obtained were
molded into a predetermined specimen by a hot press molding machine
(having the highest temperature of 210.degree. C.). The specimen
was subjected to the following Izod impact test and drop-weight
impact test in accordance with a Dupont method.
(i) Izod impact test
The Izod impact test was carried out in accordance with JIS
K7110.
(ii) Dupont method drop-weight impact test
Using a specimen (50 mm.times.50 mm.times.2 mm), the Dupont impact
strength was measured by a drop-weight impact testing equipment
(defined by JIS K5400-8, 3, 2) under the conditions of a specimen
temperature of 10.degree. C., an impact point curvature radius of
1/4 inch and an impact point receiver inner diameter of 3/2 inch,
with varying the impact point weight and the dropping height.
(6) Infrared spectrophotometry
The crosslinked structure on the surfaces of the water-insoluble
ammonium polyphosphate particles was observed by a Fourier
transform infrared spectrophotometer [trade name: FTIR-4000,
produced by Shimazu Seisakusho K.K.] in accordance with a KBr
tablet method.
Example 1
Into a Henschel mixer (trade name) were introduced 56.5% by weight
of a crystalline propylene-ethylene block copolymer (D1) [ethylene
content: 8.5% by weight, MFR (230.degree. C., 2.16 kgf): 20 g/10
min], 10% by weight of high-density polyethylene (D2) [MI
(190.degree. C., 2.16 kgf): 6.5 g/10 min, melting point (Tm):
130.degree. C., density: 0.952 g/cc] and 10% by weight of an
ethylene-propylene rubber (D3) [trade name: EP-02P, available from
Japan Synthetic Rubber Co., Ltd.], each as a thermoplastic polymer
(D), 1.0% by weight of magnesium oxide (A1) [trade name: KYOWAMAG,
available from Kyowa Kagaku K.K.] as an oxygen-containing solid
compound (A), 5% by weight of a homopolymer (B1) having a
constituent unit of 2-piperazinylene-4-morpholino-1,3,5-triazine as
a nitrogen-containing organic compound (B), 17% by weight of a
powder of ammonium polyphosphate (crystal form II) (C1) as a powder
of ammonium polyphosphate (C), and 0.2% by weight of
2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (E2) and 0.1% by weight
of calcium stearate (E3), each as an additive (E), and they were
stirred and mixed for 3 minutes. The resulting mixture was melt
kneaded at a temperature of 200.degree. C. and extruded by an
extruder (bore diameter: 30 mm), to obtain pellets of a
flame-retardant polymer composition. The pellets were molded into a
predetermined specimen. The specimen was measured on the oxygen
index and the flame retardance to evaluate the primary flame
retardance formulation. The results are set forth in Table 1.
Example 2
The procedure of Example 1 was repeated except that magnesium oxide
(A2) [trade name: KYOWAMAG, available from Kyowa Kagaku K.K.) was
used in an amount of 0.5% by weight based on the weight of the
resulting composition as the oxygen-containing solid compound (A),
to prepare pellets. Using the pellets, the oxygen index and the
flame retardance were measured in the same manner as described in
Example 1 to evaluate the primary flame retardance formulation. The
results are set forth in Table 1.
Example 3
The procedure of Example 1 was repeated except that aluminum oxide
(A2) [trade name: Alumina-A-42-3, available from Showa Denko K.K.]
was used in an amount of 3.0% by weight based on the weight of the
resulting composition as the oxygen-containing solid compound (A),
to prepare pellets. Using the pellets, the oxygen index and the
flame retardance were measured in the same manner as described in
Example 1 to evaluate the primary flame retardance formulation. The
results are set forth in Table 1.
Examples 4-9
The procedure of Example 1 was repeated except that the following
compound was used as the oxygen-containing solid compound (A), to
prepare pellets. Using the pellets, the oxygen index and the flame
retardance were measured in the same manner as described in Example
1 to evaluate the primary flame retardance formulation. The results
are set forth in Table 1.
Example 4: aluminum oxide (A2) [trade name: Alumina A-42-3,
available from Showa Denko K.K.]
Example 5: magnesium hydroxide (A3) [trade name: KISMA 5A,
available from Kyowa Kagaku K.K.]
Example 6: talc (A4)
Example 7: calcium metasilicate (A5)
Example 8: magnesium silicate (A6)
Example 9: basic magnesium carbonate (A7)
Example 10
The procedure of Example 1 was repeated except that a powder of
melamine-coated ammonium polyphosphate (C2) was used as the powder
of ammonium polyphosphate (C), to prepare pellets. Using the
pellets, the oxygen index and the flame retardance were measured in
the same manner as described in Example 1 to evaluate the primary
flame retardance formulation. The results are set forth in Table
2.
Example 11
The procedure of Example 4 was repeated except that a powder of
melamine-coated ammonium polyphosphate (C2) was used as the powder
of ammonium polyphosphate (C), to prepare pellets. Using the
pellets, the oxygen index and the flame retardance were measured in
the same manner as described in Example 4 to evaluate the primary
flame retardance formulation. The results are set forth in Table
2.
Example 12
The procedure of Example 1 was repeated except that a product (B2)
obtained by reacting cyanuric chloride with ethylenediamine in the
reaction molar ratio of 2/3 (cyanuric chloride/ethylenediamine) was
used as the nitrogen-containing organic compound (B), to prepare
pellets. Using the pellets, the oxygen index and the flame
retardance were measured in the same manner as described in Example
1 to evaluate the primary flame retardance formulation. The results
are set forth in Table 2.
Example 13
Into a Henschel mixer (trade name) were introduced 65.5% by weight
of low-density polyethylene (D4) [MI (190.degree. C., 2.16 kgf): 3
g/10 min, softening point: 96.degree. C., density: 0.942 g/cc,
trade name: PETROCEN 186, available from TOSOH CORPORATION] as a
thermoplastic polymer (D), 1.0% by weight of magnesium hydroxide
(A3) [trade name: KISMA 5A, available from Kyowa Kagaku K.K.] as an
oxygen-containing solid compound (A), 9% by weight of a homopolymer
(B1) having a constituent unit of
2-piperazinylene-4-morpholino-1,3,5-triazine as a
nitrogen-containing organic compound (B), 24% by weight of a powder
of ammonium polyphosphate (crystal form II) (C6) as a powder of
ammonium polyphosphate (C), and 0.2% by weight of
2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (E2) and 0.1% by weight
of calcium stearate (E3), each as an additive (E), and they were
stirred and mixed for 3 minutes. The resulting mixture was melt
kneaded at a temperature of 200.degree. C. and extruded by an
extruder (bore diameter: 30 mm), to obtain pellets of a
flame-retardant polymer composition. The pellets were molded into a
predetermined specimen. The specimen was measured on the oxygen
index and the flame retardance to evaluate the primary flame
retardance formulation. The results are set forth in Table 2.
Example 14
Into a Henschel mixer (trade name) were introduced 62.5% by weight
of a polystyrene resin (D5) [MI (190.degree. C., 2.16 kgf): 1.7
g/10 min, softening point: 97.degree. C., density: 1.05 g/cc, trade
name: STYRON 475S, available from Asahi Chemical Industry Co.,
Ltd.] as a thermoplastic polymer (D), 1.0% by weight of magnesium
hydroxide (A3) [trade name: KISMA 5A, available from Kyowa Kagaku
K.K.] as an oxygen-containing solid compound (A), 10% by weight of
a homopolymer (B1) having a constituent unit of
2-piperazinylene-4-morpholino-1,3,5-triazine as a
nitrogen-containing organic compound (B), 26% by weight of a powder
of ammonium polyphosphate (crystal form II) (C6) as a powder of
ammonium polyphosphate (C), and 0.2% by weight of
2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (E2) and 0.1% by weight
of calcium stearate (E3), each as an additive (E), and they were
stirred and mixed for 3 minutes. The resulting mixture was melt
kneaded at a temperature of 200.degree. C. and extruded by an
extruder (bore diameter: 30 mm), to obtain pellets of a
flame-retardant polymer composition. The pellets were molded into a
predetermined specimen. The specimen was measured on the oxygen
index and the flame retardance to evaluate the primary flame
retardance formulation. The results are set forth in Table 2.
Comparative Example 1
Into a Henschel mixer (trade name) were introduced 57.5% by weight
of a crystalline propylene-ethylene block copolymer (D1) [ethylene
content: 8.5% by weight, MFR (230.degree. C., 2.16 kgf): 20 g/10
min], 10% by weight of high-density polyethylene (D2) [MI
(190.degree. C., 2.16 kgf): 6.5 g/10 min, melting point (Tm):
130.degree. C., density: 0.952 g/cc] and 10% by weight of an
ethylene-propylene rubber (D3) [trade name: EP-02P, available from
Japan Synthetic Rubber Co., Ltd.), each as a thermoplastic polymer
(D), 5% by weight of a homopolymer (B1) having a constituent unit
of 2-piperazinylene-4-morpholino-1,3,5-triazine as a
nitrogen-containing organic compound (B), 17% by weight of a powder
of ammonium polyphosphate (crystal form II) (C6) as a powder of
ammonium polyphosphate (C), 1.0% by weight of magnesium sulfate
(A8) (solid acid) in place of the oxygen-containing solid compound
(A) used in the above examples, and 0.2% by weight of
2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (E2) and 0.1% by weight
of calcium stearate (E3), each as an additive (E), and they were
stirred and mixed for 3 minutes.
The resulting mixture was melt kneaded at a temperature of
200.degree. C. and extruded by an extruder (bore diameter: 30 mm),
to obtain pellets of a flame-retardant polymer composition. The
pellets were molded into a predetermined specimen. The specimen was
evaluated on the flame retardance. The result is set forth in Table
1.
Comparative Example 2
The procedure of Example 1 was repeated except that calcium sulfate
(A9) (solid acid) was used in place of the oxygen-containing solid
compound (A), to prepare pellets. Using the pellets, the flame
retardance was evaluated. The result is set forth in Table 1.
Comparative Example 3
The procedure of Example 1 was repeated except that 50.5% by weight
of a crystalline propylene-ethylene block copolymer (D1) [ethylene
content: 8.5% by weight, MFR (230.degree. C., 2.16 kgf): 20 g/10
min] was used as the thermoplastic polymer (D) and 7.0% by weight
of magnesium hydroxide (A5) [trade name: KISMA 5A, available from
Kyowa Kagaku K.K.] was used as the oxygen-containing solid compound
(A), to prepare pellets. Using the pellets, the flame retardance
was evaluated. The result is set forth in Table 1.
Comparative Example 4
Into a Henschel mixer (trade name) were introduced 66.5% by weight
of low-density polyethylene (D4) [MI (190.degree. C., 2.16 kgf): 3
g/10 min, softening point: 96.degree. C., density: 0.924 g/cc,
trade name: PETROCEN 186, available from TOSOH CORPORATION] as a
thermoplastic polymer (D), 9% by weight of a homopolymer (B1)
having a constituent unit of
2-piperazinylene-4-morpholino-1,3,5-triazine as a
nitrogen-containing organic compound (B), 24% by weight of a powder
of ammonium polyphosphate (crystal form II) (C6) as a powder of
ammonium polyphosphate (C), and 0.2% by weight of
2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (E2) and 0.1% by weight
of calcium stearate (E3), each as an additive (E), and they were
stirred and mixed for 3 minutes.
The resulting mixture was melt kneaded at a temperature of
200.degree. C. and extruded by an extruder (bore diameter: 30 mm),
to obtain pellets of a flame-retardant polymer composition. The
pellets were molded into a predetermined specimen. The specimen was
evaluated on the flame retardance. The result is set forth in Table
2.
Comparative Example 5
Into a Henschel mixer (trade name) were introduced 63.5% by weight
of a polystyrene resin (D5) [MI (190.degree. C., 2.16 kgf): 1.7
g/10 min, softening point: 97.degree. C., density: 1.05 g/cc, trade
name: STYRON 475S, available from Asahi Chemical Industry Co.,
Ltd.] as a thermoplastic polymer (D), 10% by weight of a
homopolymer (B1) having a constituent unit of
2-piperazinylene-4-morpholino-1,3,5-triazine as a
nitrogen-containing organic compound (B), 26% by weight of a powder
of ammonium polyphosphate (crystal form II) (C6) as a powder of
ammonium polyphosphate (C), and 0.2% by weight of
2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (E2) and 0.1% by weight
of calcium stearate (E3), each as an additive (E), and they were
stirred and mixed for 3 minutes.
The resulting mixture was melt kneaded at a temperature of
200.degree. C. and extruded by an extruder (bore diameter: 30 mm),
to obtain pellets of a flame-retardant polymer composition. The
pellets were molded into a predetermined specimen. The specimen was
evaluated on the flame retardance. The result is set forth in Table
2.
Preparation of the polymer composition of the secondary flame
retardance formulation according to the invention:
Example 15
Into a 5-liter kneader (equipped with a heating-kneading means and
a deaeration means) were introduced 1,000 g of a powder of
melamine-coated ammonium polyphosphate (C2) and 203 g of a
formaldehyde aqueous solution (concentration: 37%), and they were
mixed at room temperature for 30 minutes. Then, the resulting
mixture was heated to 100.degree. C. to perform reaction for 1 hour
with stirring, so as to obtain 1,035 g of a powder of
water-insoluble ammonium polyphosphate (C3). This water-insoluble
ammonium polyphosphate powder was prepared by crosslinking the
melamine molecules present on the surface of the melamine-coated
ammonium polyphosphate (C2) powder (starting material) with the
aldehyde group (--CHO) so as to water-insolubilize the
melamine-coated ammonium polyphosphate (C2) powder.
Into a Henschel mixer (trade name) were introduced 20% by weight of
the water-insoluble ammonium polyphosphate (C3) powder, 10% by
weight of a homopolymer (B1) having a constituent unit of
2-piperazinylene-4-morpholino-1,3,5-triazine as a
nitrogen-containing organic compound (B), 60.5% by weight of a
propylene-ethylene crystalline copolymer (D1) [ethylene content:
8.5% by weight, MFR (230.degree. C., 2.16 kgf): 20 g/10 min] as a
thermoplastic resin (D), and 0.2% by weight of
2,6-di-t-butyl-p-cresol (BHT) (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (DMyTDP) (E2) and 0.1%
by weight of calcium stearate (CS) (E3), each as an additive (E),
and they were stirred and mixed for 3 minutes.
The resulting mixture was melt kneaded at a temperature of
200.degree. C. and extruded by an extruder (bore diameter: 30 mm),
to obtain pellets of a flame-retardant polymer composition. The
flame-retardant polymer composition pellets thus obtained were
dried at 100.degree. C. for 3 hours and molded into a predetermined
specimen using an injection molding machine (highest temperature of
cylinder: 220.degree. C.). The specimen was measured with regard to
surface electrical resistance before and after immersion in hot
water, bleed resistance lasting period under conditions of high
temperature and high humidity and flame retardance to evaluate the
secondary flame retardance formulation. The results are set forth
in table 3.
Examples 16-18
The procedure of Example 15 was repeated except that the following
compound was used as the nitrogen-containing organic compound (B),
to prepare pellets of a flame-retardant polymer composition. The
pellets were molded into a predetermined specimen. The specimen was
measured with the regard to surface electrical resistance before
and after immersion in hot water, bleed resistance lasting period
under conditions of high temperature and high humidity and flame
retardance to evaluate the secondary flame retardance formulation.
The results are set forth in table 3.
Example 16: a homopolymer (B2) having
2-piperazinylene-4-N,N-bis(2-hydroxyethyl)amino-1,3,5-triazine as
its constituent unit
Example 17: a copolymer (B3) of
2-piperazinylene-4-morpholino-1,3,5-triazine and
2-piperazinylene-4-N,N-bis(2-hydroxyethyl)amino-1,3,5-triazine in
the equimolar ratio
Example 18: a reaction product (B4) of cyanuric chloride (2 mol)
with ethylenediamine (3 mol)
Example 19
Into a 5-liter glass flask (equipped with a heating-stirring means
and a deaeration means) were introduced 1,000 g of a powder of
melamine-coated ammonium polyphosphate (C2) and 900 g of toluene.
To the flask were further introduced 132 g of hexamethylene
diisocyanate and 2.6 g of NIKKAOCTHIK"SN" catalyst, and the content
in the flask was mixed at room temperature. Then, the temperature
in the glass flask was elevated to reflux temperature, and the
content was mixed for 2 hours at the same temperature. After
cooling and filtering, the content was transferred into a dryer and
dried at 100.degree. C. for 1 hour, to obtain 1,080 g of a powder
of water-insoluble ammonium polyphosphate (C4). This
water-insoluble ammonium polyphosphate powder was prepared by
uniformly crosslinking the melamine molecules present on the
surface of the melamine-coated ammonium polyphosphate (C2) powder
(starting material) with the isocyanate group (--NCO).
Pellets of a flame-retardant polymer composition were prepared in
the same manner as described in Example 1 except that the
water-insoluble ammonium polyphosphate (C4) was used in an amount
of 20% by weight. The pellets were molded into a specimen. The
specimen was measured with regard to surface electrical resistance
before and after immersion in hot water, bleed resistance lasting
period under conditions of high temperature and high humidity and
flame retardance to evaluate the secondary flame retardance
formulation. The results are set forth in table 3.
Example 20
Into a 5-liter glass flask (equipped with a heating-stirring means
and a deaeration means) were introduced 1,000 g of a powder of
melamine-coated ammonium polyphosphate (C2), 909 g of water and 91
g of methanol. To the flask was further introduced 92 g of glyoxal
(concentration: 49%), and the content in the flask was mixed at
room temperature. Then, the temperature in the glass flask was
elevated to reflux temperature, and the content was stirred for 2
hours. After cooling, the content was filtered and transferred into
a dryer, followed by drying at 100.degree. C. for 1 hour, to obtain
1,025 g of a powder of water-insoluble ammonium polyphosphate
(C5).
This water-insoluble ammonium polyphosphate powder was prepared by
uniformly crosslinking the melamine molecules present on the
surface of the melamine-coated ammonium polyphosphate (C2) powder
(starting material) with the aldehyde group.
Pellets of a flame-retardant polymer composition were prepared in
the same manner as described in Example 1 except that the
water-insoluble ammonium polyphosphate (C5) powder was used in an
amount of 20% by weight. The pellets were molded into a specimen.
The specimen was measured with regard to surface electrical
resistance before and after immersion in hot water, bleed
resistance lasting period under conditions of high temperature and
high humidity and flame retardance to evaluate the secondary flame
retardance formulation. The results are set forth in table 3.
Example 21
The procedure of Example 1 was repeated except for using 66.5% by
weight of low-density polyethylene (D2) [trade name: PETROCEN 186,
available from TOSOH CORPORATION] as a thermoplastic resin (D), 24%
by weight of a powder of the water-insoluble ammonium polyphosphate
(C3), 9% by weight of a homopolymer (B1) having a constituent unit
of 2-piperazinylene-4-morpholino-1,3,5-triazine as a
nitrogen-containing organic compound (B), and 0.2% by weight of
2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (E2) and 0.1% by weight
of calcium stearate (E3), each as an additive (E), to prepare
pellets of a flame-retardant polymer composition. The pellets were
molded into a specimen. The specimen was measured with regard to
surface electrical resistance before and after immersion in hot
water, bleed resistance lasting period under conditions of high
temperature and high humidity and flame retardance to evaluate the
secondary flame retardance formulation. The results are set forth
in table 3.
Example 22
The procedure of Example 1 was repeated except for using 63.5% by
weight of a polystyrene resin (D3) [trade name: STYRON 475S,
available from Asahi chemical Industry Co., Ltd.] as a
thermoplastic resin (D), 26% by weight of a powder of the
water-insoluble ammonium polyphosphate (C3), 10% by weight of a
homopolymer (B1) having a constituent unit of
2-piperazinylene-4-morpholino-1,3,5-triazine as a
nitrogen-containing organic compound (B), and 0.2% by weight of
2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (E2) and 0.1% by weight
of calcium stearate (E3), each as an additive (E), to prepare
pellets of a flame-retardant polymer composition. The pellets were
molded into a specimen. The specimen was measured with regard to
surface electrical resistance before and after immersion in hot
water, bleed resistance lasting period under conditions of high
temperature and high humidity and flame retardance to evaluate
secondary flame retardance formulation. The results are set forth
in table 3.
Comparative Example 6
The procedure of Example 1 was repeated except for using 20% by
weight of a powder of ammonium polyphosphate (crystal form II) (C6)
in place of the water-insoluble ammonium polyphosphate powder (C3),
to prepare pellets of a flame-retardant polymer composition. The
pellets were molded into a specimen. The specimen was measured with
regard to surface electrical resistance before and after immersion
in hot water, bleed resistance lasting period under conditions of
high temperature and high humidity and flame retardance. The
results are set forth in table 3.
Comparative Example 7
The procedure of Example 1 was repeated except for using 20% by
weight of a powder of commercially available ammonium polyphosphate
(C7) [trade name: SUMISAFE-P, available from Sumitomo Chemical Co.,
Ltd.] in place of the water-insoluble ammonium polyphosphate powder
(C3), to prepare pellets of a flame-retardant polymer composition.
The pellets were molded into a specimen. The specimen was measured
with regard to surface electrical resistance before and after
immersion in hot water, bleed resistance lasting period under
conditions of high temperature and high humidity and the flame
retardance. The results are set forth in table 3.
Comparative Example 8
Into a 5-liter glass flask (equipped with a heating-stirring means
and a deaeration means) were introduced 900 g of a powder of
ammonium polyphosphate (crystal form II) (C6) and a mixed solvent
consisting of 600 g of water and 400 g of methanol, and they were
stirred and mixed at room temperature. To the flask was further
introduced a methylol melamine aqueous solution separately prepared
(i.e., aqueous solution of a reaction product obtained by mixing
and stirring 100 g of melamine and 160 g of a formaldehyde aqueous
solution (concentration: 37%) at 70.degree. C. for 1 hour) to
adjust pH of the system to 4.5, and the reaction was performed at
75.degree. C. for 2 hours to resinify the methylol melamine.
After cooling, the content in the flask was filtered and
transferred into a dryer, followed by drying at 100.degree. C. for
1 hour, to obtain 1,030 g of resin-attached ammonium polyphosphate
(C8). This resin-attached ammonium polyphosphate was prepared by
attaching the melamine resin onto the surface of the ammonium
polyphosphate (crystal form II) powder (C6).
Pellets of a flame-retardant polymer composition were prepared in
the same manner as described in Example 15 except that 20% by
weight of the melamine resin-attached ammonium polyphosphate (C8)
was used in place of the water-insoluble ammonium polyphosphate
(C3). The pellets were molded into a specimen. The specimen was
measured surface electrical resistance before and after immersion
in hot water, bleed resistance lasting period under conditions of
high temperature and high humidity and flame retardance. The
results are set forth in table 3.
Example 23
Into a Henschel mixer (trade name) were introduced 56.5% by weight
of a crystalline propylene-ethylene block copolymer (D1) [ethylene
content: 8.5% by weight, MFR (230.degree. C., 2.16 kgf): 20 g/10
min], 10% by weight of high-density polyethylene (D2) [MI
(190.degree. C., 2.16 kgf): 6.5 g/10 min, melting point (Tm) :
130.degree. C., density: 0.952 g/cc] and 10% by weight of an
ethylene-propylene rubber (D3) [trade name: EP-02P, available from
Japan Synthetic Rubber Co., Ltd.], each as a thermoplastic polymer
(D), 0.5% by weight of magnesium oxide (A1) [trade name: KYOWAMAG,
available from Kyowa Kagaku K.K.] as an oxygen-containing solid
compound (A), 5% by weight of a homopolymer (B1) having a
constituent unit of 2-piperazinylene-4-morpholino-1,3,5-triazine as
a nitrogen-containing organic compound (B), 17% by weight of a
powder of water-insoluble ammonium polyphosphate (C3) having been
crosslinked by the reaction with formaldehyde as a powder of
ammonium polyphosphate (C), and 0.2% by weight of
2,6-di-t-butyl-p-cresol (E1), 0.2% by weight of
dimyristyl-.beta.,.beta.'-thiodipropionate (E2) and 0.1% by weight
of calcium stearate (E3), each as an additive (E), and they were
stirred and mixed for 3 minutes. The resulting mixture was melt
kneaded at a temperature of 200.degree. C. and extruded by an
extruder (bore diameter: 30 mm), to obtain pellets of a
flame-retardant polymer composition. The pellets were molded into a
predetermined specimen. The specimen was measured with regard to
oxygen index and flame retardance to evaluate the primary flame
retardance formulation. The results are set forth in Table 4.
Example 24
The procedure of Example 23 was repeated except for using 1.0% by
weight of aluminum oxide as the oxygen-containing solid compound
(A), to prepare pellets. Using the pellets, the oxygen index and
the flame retardance were measured in the same manner as described
in Example 1 to evaluate the primary flame retardance formulation.
The results are set forth in Table 4.
Example 25
The procedure of Example 23 was repeated except for using 2.0% by
weight of magnesium hydroxide (A1) as the oxygen-containing solid
compound (A), 5% by weight of a product (B2) obtained by reacting
cyanuric chloride with ethylenediamine in the reaction molar ratio
of 2/3 (cyanuric chloride/ethylenediamine) as the
nitrogen-containing organic compound (B) and 17% by weight of a
powder of water-insoluble ammonium polyphosphate (C3) having been
crosslinked by the reaction with formaldehyde as the powder of
ammonium polyphosphate (C), to prepare pellets. Using the pellets,
the oxygen index and the flame retardance were measured in the same
manner as described in Example 1 to evaluate the primary flame
retardance formulation. The results are set forth in Table 4.
Example 26
The procedure of Example 23 was repeated except for using 1.0% by
weight of magnesium hydroxide (A1) as the oxygen-containing solid
compound (A), 5% by weight of a product (B2) obtained by reacting
cyanuric chloride with ethylenediamine in the reaction molar ratio
of 2/3 (cyanuric chloride/ethylenediamine) as the
nitrogen-containing organic compound (B) and 17% by weight of a
powder of water-insoluble ammonium polyphosphate (C3) having been
crosslinked by the reaction with formaldehyde as the powder of
ammonium polyphosphate (C), to prepare pellets. Using the pellets,
the oxygen index and the flame retardance were measured in the same
manner as described in Example 1 to evaluate the primary flame
retardance formulation. The results are set forth in Table 4.
Example 27
The procedure of Example 23 was repeated except for using 2.0% by
weight of aluminum oxide (A1) as the oxygen-containing solid
compound (A), 5% by weight of a product (B2) obtained by reacting
cyanuric chloride with ethylenediamine in the reaction molar ratio
of 2/3 (cyanuric chloride/ethylenediamine) as the
nitrogen-containing organic compound (B) and 17% by weight of a
powder of water-insoluble ammonium polyphosphate (C3) having been
crosslinked by the reaction with formaldehyde as the powder of
ammonium polyphosphate (C), to prepare pellets. Using the pellets,
the oxygen index and the flame retardance were measured in the same
manner as described in Example 1 to evaluate the primary flame
retardance formulation. The results are set forth in Table 4.
Example 28
Into a 5-liter kneader (equipped with a heating-mixing means and a
deaeration means) were introduced 1,000 g of melamine-coated
ammonium polyphosphate (C2) and 64.3 g of a formaldehyde aqueous
solution (concentration: 37% by weight), and they were mixed at
room temperature. Then, the temperature of the kneader was elevated
to 100.degree. C. and kept at the same temperature for 1 hour with
deaerating, to obtain 1,010 g of water-insoluble ammonium
polyphosphate (C3) in which the melamine molecules present on the
surface of the powder of the melamine-coated ammonium polyphosphate
(C2) were crosslinked with the aldehyde group (--CHO) to
water-insolubilize the melamine-coated ammonium polyphosphate (C2).
The mean particle diameter of the water-insoluble ammonium
polyphosphate (C3) and the content of the water-soluble component
were measured. The results are set forth in Table 5.
Using the water-insoluble ammonium polyphosphate (C3), a
flame-retardant polymer composition was prepared in the same manner
as described in Example 15. From the composition, a specimen was
formed. The specimen was measured with regard to the Izod impact
strength and the Dupont impact strength. The results are set forth
in Table 5.
Example 29
The procedure of Example 23 was repeated except for varying the
amount of the formaldehyde aqueous solution to 129 g, to obtain
1,020 g of water-insoluble ammonium polyphosphate (C3). The mean
particle diameter of the water-insoluble ammonium polyphosphate
(C3) and the content of the water-soluble component were measured.
The results are set forth in Table 5.
Using the water-insoluble ammonium polyphosphate (C3), a
flame-retardant polymer composition was prepared in the same manner
as described in Example 15. From the composition, a specimen was
formed. The specimen was measured with regard to the Izod impact
strength and the Dupont impact strength. The results are set forth
in Table 5.
Example 30
Into a 5-liter kneader (equipped with a heating-mixing means and a
deaeration means) were introduced 1,000 g of melamine-coated
ammonium polyphosphate (C2) and 64.3 g of a formaldehyde aqueous
solution (concentration: 37% by weight), and they were mixed at
room temperature. Then, the temperature of the kneader was elevated
to 150.degree. C. and kept at the same temperature for 0.5 hour
with deaerating, to obtain 1,010 g of water-insoluble ammonium
polyphosphate (C3) in which the melamine molecules present on the
surface of the powder of the melamine-coated ammonium polyphosphate
(C2) were crosslinked with the aldehyde group (--CHO) so as to
water-insolubilize the melamine-coated ammonium polyphosphate (C2).
The mean particle diameter of the water-insoluble ammonium
polyphosphate (C3) and the content of the water-soluble component
were measured. The results are set forth in Table 5.
Example 31
Into a 5-liter glass flask (equipped with a heating-mixing means
and a deaeration means) were introduced 1,000 g of melamine-coated
ammonium polyphosphate (C2), 64.3 g of a formaldehyde aqueous
solution (concentration: 37% by weight), 909 g of water and 90.9 g
of methyl alcohol, and they were mixed at room temperature. Then,
the flask was heated to 80.degree. C. and kept at the same
temperature for 1 hour in the reflux state, followed by filtration,
to obtain a solid. The solid was transferred into a dryer and dried
at 100.degree. C. for 1 hour to obtain 1,010 g of water-insoluble
ammonium polyphosphate (C3). The mean particle diameter of the
water-insoluble ammonium polyphosphate (C3) and the content of the
water-soluble component were measured. The results are set forth in
Table 5.
Example 32
The procedure of Example 26 was repeated except for varying the
amount of the formaldehyde aqueous solution to 129 g, to obtain
1,020 g of water-insoluble ammonium polyphosphate (C3). The mean
particle diameter of the water-insoluble ammonium polyphosphate
(C3) and the content of the water-soluble component were measured.
The results are set forth in Table 5.
Example 33
Into a 5-liter glass flask (equipped with a heating-mixing means
and a deaeration means) were introduced 1,000 g of melamine-coated
ammonium polyphosphate (C2), 92 g of glyoxal (concentration: 49% by
weight) and 90.9 g of methyl alcohol, and they were mixed at room
temperature. Then, the flask was heated to 80.degree. C. and kept
at the same temperature for 1 hour in the reflux state, followed by
filtration, to obtain a solid. The solid was transferred into a
dryer and dried at 100.degree. C. for 1 hour to obtain 1,025 g of
water-insoluble ammonium polyphosphate (C4). The mean particle
diameter of the water-insoluble ammonium polyphosphate (C4) and the
content of the water-soluble component were measured. The results
are set forth in Table 5.
Example 34
Into a 5-liter glass flask (equipped with a heating-mixing means
and a deaeration means) were introduced 1,000 g of melamine-coated
ammonium polyphosphate (C2), 92 g of 1,6-diisocyanatehexane, 2.6 g
of NIKKAOCTHIK "SN" and 900 g of toluene, and they were mixed at
room temperature. Then, the flask was heated to 120.degree. C. and
kept at the same temperature for 2 hours in the reflux state,
followed by filtration, to obtain a solid. The solid was
transferred into a dryer and dried at 120.degree. C. for 1 hour to
obtain 1,010 g of water-insoluble ammonium polyphosphate (C5). The
mean particle diameter of the water-insoluble ammonium
polyphosphate (C5) and the content of the water-soluble component
were measured. The results are set forth in Table 5.
Example 35
Into a 5-liter glass flask (equipped with a heating-mixing means
and a deaeration means) were introduced 900 g of melamine-coated
ammonium polyphosphate (C2) and a mixed solvent consisting of 600 g
of water and 400 g of methyl alcohol, and they were mixed at room
temperature. Then, a methylol melamine solution separately prepared
[solution obtained by adding 160 g of a formaldehyde solution
(concentration: 37% by weight) to 100 of melamine and dissolving
the melamine in the solution with stirring for 1 hour) was added,
and pH of the system was adjusted to 4.5.
The resulting mixture was reacted at 75.degree. C. for 2 hours to
resinify the methylol melamine. Then, the reaction system was
cooled to room temperature, followed by filtration, to obtain a
solid. The solid was transferred into a dryer and dried at
100.degree. C. for 1 hour, to obtain 1,025 g of water-insoluble
ammonium polyphosphate (C5). This water-insoluble ammonium
polyphosphate (C5) was prepared by resinifying the melamine
molecules present on the surface of the melamine-coated ammonium
polyphosphate powder (2) through crosslinking reaction to
water-insolubilize the melamine-coated ammonium polyphosphate
powder (2). The mean particle diameter of the water-insoluble
ammonium polyphosphate (C5) and the content of the water-soluble
component were measured. The results are set forth in Table 5.
Comparative Example 9
A mixture of 1,150 g.mol of ammonium phosphate (C1), 601 g of urea
and 631 g of melamine was introduced into a kneader (equipped with
a heating means and kept at 270.degree. C.) was introduced as a
starting material, and it was burned at the same temperature for
1.5 hours in an ammonia gas atmosphere, to obtain 1,540 g of
modified ammonium polyphosphate (C10). The mean particle diameter
of the modified ammonium polyphosphate (C10) and the content of the
water-soluble component were measured. The results are set forth in
Table 5.
Using the modified ammonium polyphosphate (C10), a flame-retardant
polymer composition was prepared in the same manner as described in
Example 15. From the composition, a specimen was formed. The
specimen was measured with regard to the Izod impact strength and
the Dupont impact strength. The results are set forth in Table
5.
Comparative Example 10
Into a 5-liter glass flask (equipped with a heating-stirring means
and a deaeration means) was initially introduced a mixed solvent
consisting of 1,200 g of water and 300 g of methyl alcohol. To the
flask were further introduced 1,000 g of commercially available
ammonium polyphosphate (C7) [trade name: EXOLIT-422, available from
Hechist Co.), 100 g of a melamine/formaldehyde precondensate [trade
name: NIKKARESIN S-305, available from Nippon Carbide Industries
Co., Ltd.) and 5 g of a curing catalyst [trade name: Catanit A,
available from Nitto Chemical Industry Co., Ltd.) to prepare a
suspension.
The suspension was heated to 83.degree. C. and reacted at the same
temperature for 1 hour. Then, the reaction solution was cooled and
filtered to obtain a solid. The solid was washed with methyl
alcohol and dried at 100.degree. C. in a nitrogen atmosphere. Thus,
1,050 g of ammonium polyphosphate (C8) having been coated with a
melamine-formaldehyde resin on the surface was obtained. The mean
particle diameter of the ammonium polyphosphate (C8) and the
content of the water-soluble component were measured. The results
are set forth in Table 5.
Using the ammonium polyphosphate (C8), a flame-retardant polymer
composition was prepared in the same manner as described in Example
15. From the composition, a specimen was formed. The specimen was
measured with regard to the Izod impact strength and the Dupont
impact strength. The results are set forth in Table 5.
Comparative Example 11
Into a 5-liter glass flask (equipped with a heating-stirring means
and a deaeration means) were introduced 1,000 g of commercially
available ammonium polyphosphate (C7) [trade name: EXOLIT-422,
available from Hechist Co.) and a mixed solvent consisting of 120 g
of water and 300 g of methyl alcohol, and they were mixed at room
temperature.
Then, a methylol melamine solution separately prepared [solution
obtained by adding 160 g of formalin (concentration: 37% by weight)
to 100 of melamine and dissolving the melamine in the solution with
stirring at 70.degree. C. for 1 hour] was added, and pH of the
system was adjusted to 4.5. The resulting mixture was reacted at
83.degree. C. for 1 hour to resinify the methylol melamine. After
cooling, the reaction solution was dried at 100.degree. C. in a
nitrogen atmosphere. Thus, 1,080 g of ammonium polyphosphate (C8)
having been coated with a melamine-formaldehyde resin on the
surface was obtained. The mean particle diameter of the ammonium
polyphosphate (C8) and the content of the water-soluble component
were measured. The results are set forth in Table 5.
Comparative Example 12
Into a 5-liter kneader (equipped with a heating-mixing means and a
deaeration means) were introduced 1,000 g of melamine-coated
ammonium polyphosphate (C2) and 64.3 g of a formaldehyde aqueous
solution (concentration: 37% by weight), and they were mixed at
room temperature. Then, the flask was heated to 50.degree. C. and
kept at the same temperature for 1 hour with deaerating. As a
result, a crosslinked structure was not formed on the surface of
the melamine-coated ammonium polyphosphate (C2) powder. The mean
particle diameter of the melamine-coated ammonium polyphosphate
(C2) and the content of the water-soluble component were measured.
The results are set forth in Table 5.
Comparative Example 13
Into a 5-liter kneader (equipped with a heating-mixing means and a
deaeration means) were introduced 1,000 g of melamine-coated
ammonium polyphosphate (C2) and 64.3 g of a formaldehyde aqueous
solution (concentration: 37% by weight), and they were mixed at
room temperature. Then, the kneader was heated to 250.degree. C.
and kept at the same temperature for 1 hour with deaerating. As a
result, it was confirmed that though a crosslinked structure was
formed on the surface of the melamine-coated ammonium polyphosphate
(C2) powder, elimination of ammonia molecules from the crosslinked
structure formed on the surface of the powder took place. That is,
the resulting powder had no hydrolytic stability of the desired
level. The mean particle diameter of the powder obtained and the
content of the water-soluble component were measured. The results
are set forth in Table 5.
Comparative Example 14
Into a 5-liter kneader (equipped with a heating-mixing means and a
deaeration means) were introduced 1,000 g of melamine-coated
ammonium polyphosphate (C2), 6.4 g of a formaldehyde aqueous
solution (concentration: 37% by weight), 909 g of water and 90.9 g
of methyl alcohol, and they were mixed at room temperature. Then,
the kneader was heated to 100.degree. C. and kept at the same
temperature for 1 hour with deaerating, followed by filtration.
Thus, 1,002 g of a powder of water-insoluble ammonium polyphosphate
(C11) in which a crosslinked structure was formed among the
melamine molecules present on the surface of the melamine-coated
ammonium polyphosphate (C2) powder was obtained. The mean particle
diameter of the powder (C11) and the content of the water-soluble
component were measured. The results are set forth in Table 5.
Comparative Example 15
Into a 5-liter kneader (equipped with a heating-mixing means and a
deaeration means) were introduced 1,000 g of melamine-coated
ammonium polyphosphate (C2), 6.4 g of a formaldehyde aqueous
solution (concentration: 37% by weight), 909 g of water and 90.9 g
of methyl alcohol, and they were mixed at room temperature. Then,
the kneader was heated to 80.degree. C. and kept at the same
temperature for 1 hour in the reflux state, followed by filtration,
to obtain a solid. The solid was transferred into a dryer and dried
at 100.degree. C. for 1 hour. Thus, 1,002 g of a powder of
water-insoluble ammonium polyphosphate (C11) in which a crosslinked
structure was formed among the melamine molecules present on the
surface of the melamine-coated ammonium polyphosphate (C2) powder
was obtained. The mean particle diameter of the powder (C11) and
the content of the water-soluble component were measured. The
results are set forth in Table 5.
Comparative Example 16
Into a 5-liter bench kneader (equipped with a heating-mixing means
and a deaeration means) was introduced a mixture consisting of 660
g (5 mol) of diammonium phosphate and 710 g (5 mol) of phosphorus
pentaoxide with keeping a nitrogen gas atmosphere, and the mixture
was stirred for 20 minutes. Then, to the mixture was added 195 g of
an urea aqueous solution (concentration: 76.9% by weight) by
spraying, and they were burned at 270.degree. C. for 2.5 hours in
an ammonia atmosphere to obtain 1,460 g of ammonium polyphosphate
(crystal form II) (C6). The mean particle diameter of the powder
(C6) and the content of the water-soluble component were measured.
The results are set forth in Table 5.
Comparative Example 17
Into a 5-liter kneader (preheated to 280.degree. C.) were
introduced 1,800 g of an ammonium polyphosphate powder prepared in
accordance with Comparative Example 16 and 200 g of melamine, and
they were mixed under heating at 280.degree. C. This mixing was
carried out without varying the form of the starting ammonium
polyphosphate, and as a result, 2,000 g of melamine-coated ammonium
polyphosphate (C6) was obtained. The mean particle diameter of the
powder (C6) and the content of the water-soluble component were
measured. The results are set forth in Table 5.
Results of measurement
The ammonium polyphosphate powder obtained in each of Examples 28
to 35 and Comparative Examples 9 to 17 was measured on the mean
particle diameter and the hydrolytic stability. The results are set
forth in Table 5.
In addition to the measurement of the mean particle diameter, the
ammonium polyphosphate powder obtained in each of Example 28,
Example 29, Comparative Example 9 and Comparative Example 10 was
molded into a specimen, and the specimen was subjected to the Izod
impact test and the Dupont method drop-weight impact test. The
results are set forth in Table 5.
The powder of the water-insoluble ammonium polyphosphate (C3)
obtained in Example 28 was observed by the infrared
spectrophotometry, and the result is shown in FIG. 1. The powder of
the melamine-coated ammonium polyphosphate (C2) used as a starting
material was observed by the infrared spectrophotometry, and the
result is shown in FIG. 2.
FIG. 1 and FIG. 2 are each an infrared spectrum of the surface of
the water-insoluble ammonium polyphosphate powder. In both figures,
the wave number is plotted as abscissa (unit: cm.sup.-1) and the
transmittance of the infrared rays is plotted as ordinate.
In FIG. 1, absorption at 1,180 cm.sup.-1 caused by the methylene
bond derived from the crosslinked structure on the particle surface
is observed. This absorption is caused by the twisting and wagging
vibration of the C--H bond.
FIG. 2 is an infrared spectrum of the surface of the
water-insoluble melamine-coated ammonium polyphosphate powder. In
FIG. 2, absorption at 1,180 cm.sup.-1 observed in FIG. 1 is not
observed.
TABLE 1 ______________________________________ Component of
Flame-retardant Resin Composition Mean particle B C Amount diameter
B1 B2 C1 C2 Kind % (.mu.m) % % % %
______________________________________ Ex.1 Magnesium 1.0 5.6 5 --
17 -- oxide Ex.2 Magnesium 0.5 5.6 5 -- 17 -- oxide Ex.3 Aluminum
3.0 3.7 5 -- 17 -- oxide Ex.4 Aluminum 1.0 3.7 5 -- 17 -- oxide
Ex.5 Magnesium 1.0 1.7 5 -- 17 -- hydroxide Ex.6 Talc 1.0 2.8 5 --
17 -- Ex.7 Calcium 1.0 4.3 5 -- 17 -- metasilicate Ex.8 Magnesium
1.0 1.2 5 -- 17 -- silicate Ex.9 Basic 1.0 2.4 5 -- 17 -- magneisum
carbonate Comp. Magnesium 1.0 un- 5 -- 17 -- Ex.1 sulfate
measurable Comp. Calcium 1.0 un- 5 -- 17 -- Ex.2 sulfate measurable
Comp. Magnesium 7.0 1.7 5 -- 17 -- Ex.3 hydroxide
______________________________________ Flame Retardance Component
of Flame-retardant Oxygen Resin Composition Index UL D (O.I.) 94V
D1 D2 D3 Addit- 3.0 mm- 1.2 mm- % % % D4 D5 ives thick thick
______________________________________ Ex.1 56.5 10 10 -- -- 0.5
33.2 V-O Ex.2 57.0 10 10 -- -- 0.5 32.0 V-O Ex.3 54.5 10 10 -- --
0.5 34.3 V-O Ex.4 56.5 10 10 -- -- 0.5 33.8 V-O Ex.5 56.5 10 10 --
-- 0.5 32.5 V-O Ex.6 56.5 10 10 -- -- 0.5 33.0 V-O Ex.7 56.5 10 10
-- -- 0.5 32.8 V-O Ex.8 56.5 10 10 -- -- 0.5 32.1 V-O Ex.9 56.5 10
10 -- -- 0.5 33.2 V-O Comp. 56.5 10 10 -- -- 0.5 30.2 not Ex.1
examined Comp. 56.5 10 10 -- -- 0.5 29.0 not Ex.2 examined Comp.
50.5 10 10 -- -- 0.5 21.0 not Ex.3 examined
______________________________________ B1: Homopolymer having
2piperazinylene-4-morpholino-1,3,5-triazine as its consitutent unit
(decomposition temperature: about 304.degree. C., true density: 1.3
g/cc) C1: Ammonium polyphosphate (crystal form II) D1:
Propyleneethylene block copolymer [ethylene content: 8.5 wt. %, MFR
(230.degree. C., 2.16 kgf): 20 g/10 min D2: Polyethylene resin
[MI(190.degree. C., 2.16 kgf): 6.5 g/10 min, density: 0.952 g/cc,
melting point(Tm): 130.degree. C. D3: Ethylenepropylene rubber
[trade name: EP02, available from Japan Synthetic Rubber Co.,
Ltd.
TABLE 2 ______________________________________ Component of
Flame-retardant Resin Composition Mean particle B C Amount diameter
B1 B2 C1 C2 Kind % (.mu.m) % % % %
______________________________________ Ex.10 Magnesium 1.0 5.6 5 --
-- 17 oxide Ex.11 Aluminum 1.0 3.7 5 -- -- 17 oxide Ex.12 Aluminum
1.0 3.7 -- 5 17 -- oxide Ex.13 Magnesium 1.0 1.7 9 -- 24 --
hydroxide Ex.14 Magnesium 1.0 1.7 10 -- 26 -- hydroxide Comp. -- --
-- 9 -- 24 -- Ex.4 Comp. -- -- -- 10 -- 26 -- Ex.5
______________________________________ Flame Retardance Component
of Flame-retardant Oxygen Resin Composition Index UL D (O.I.) 94V
D1 D2 D3 Addit- 3.0 mm- 1.2 mm- % % % D4 D5 ives thick thick
______________________________________ Ex.10 56.5 10 10 -- -- 0.5
33.7 V-O Ex.11 56.5 10 10 -- -- 0.5 35.0 V-O Ex.12 56.5 10 10 -- --
0.5 34.7 V-O Ex.13 -- -- -- 65.5 -- 0.5 37.5 V-O Ex.14 -- -- -- --
62.5 0.5 33.4 V-O Comp. -- -- -- 66.5 -- 0.5 35.0 not Ex.4 examined
Comp. -- -- -- -- 63.5 0.5 30.6 not Ex.5 examined
______________________________________ B1 and C1 are the same as in
Table 1. B2: Reaction product obtained by reacting cyanuric
chloride with ethylenediamine in the molar ratio of 2/3 (cyanuric
chloride/ethylenediamine) C2: Melaminecoated ammonium polyphosphate
D1, D2 and D3 are the same in Table 1. D4: Lowdensity polyethylene
[MI(190.degree. C., 2.16 kgf): 3 g/10 min, density: 0.924 g/cc,
trade name: PETROCEN 186, available from Toso Corporation D5:
Polystyrene resin [MI(190.degree. CC., 2.16 kgf): 1.7 g/10 min,
density: 1.05 g/cc, trade name: STYRON 475S, available from Asahi
Chemica Industry Co., Ltd.
TABLE 3
__________________________________________________________________________
Flame-retartdant Polymer Composition Kind and Amount of Components
(% by wt.) Amount Amount Amount Additive Kind (% by wt.) Kind (% by
wt.) Kind (% by wt.) Amount
__________________________________________________________________________
Ex.15 C3 20 B1 10 D1 69.5 0.5 Ex.16 C3 20 B2 10 D1 69.5 0.5 Ex.17
C3 20 B3 10 D1 69.5 0.5 Ex.18 C3 20 B4 10 D1 69.5 0.5 Ex.19 C4 20
B1 10 D1 69.5 0.5 Ex.20 C5 20 B1 10 D1 69.5 0.5 Ex.21 C3 24 B4 9 D2
66.5 0.5 Ex.22 C3 26 B1 10 D3 63.5 0.5 Comp. C6 20 B1 10 D1 69.5
0.5 Ex.6 Comp. C7 20 B1 10 D1 69.5 0.5 Ex.7 Comp. C8 20 B1 10 D1
69.5 0.5 Ex.8
__________________________________________________________________________
Properties and Evaluations of Molded Articles from the
Flame-retardant Polymer Composition Bleed Resistance Lasting Period
under Flame High Temper. Retard- Surface Electrical Resistance and
High General ance of Hot Water Treatment Humidity Evalu- UL94V
Before treat. (.OMEGA.) After treat. (.OMEGA.) (days) ation 1.6 mm
__________________________________________________________________________
Ex.15 5.9 .times. 10.sup.17 8.8 + 10.sup.17 40 days or E V-O more
Ex.16 7.3 .times. 10.sup.16 6.1 + 10.sup.16 30 days G V-O Ex.17 3.5
.times. 10.sup.16 4.1 + 10.sup.16 40 days or E V-O more Ex.18 9.3
.times. 10.sup.16 2.2 + 10.sup.16 40 days or E V-O more Ex.19 2.9
.times. 10.sup.16 7.7 + 10.sup.16 30 days G V-O Ex.20 2.8 .times.
10.sup.16 3.7 + 10.sup.16 30 days G V-O Ex.21 6.9 .times. 10.sup.16
7.1 + 10.sup.17 40 days or E V-O more Ex.22 2.4 .times. 10.sup.16
unmeasurable* 30 days G V-O Comp. 4.0 .times. 10.sup.17 6.7 +
10.sup.10 14 days or B V-O Ex.6 less Comp. 2.7 .times. 10.sup.16
1.6 + 10.sup.9 7 days or W V-O Ex.7 less Comp. 8.7 .times.
10.sup.16 3.4 + 10.sup.10 14 days or B V-O Ex.8 less
__________________________________________________________________________
C3: HCHOcrosslinked waterinsoluble ammonium polyphosphate C4:
NCOcrosslinked waterinsoluble ammonium polyphosphate C5:
Glyoxalcrosslinbked waterinsoluble ammonium polyphosphate C6:
Ammonium polyphosphate (crystal form II) C7: Commercially available
amonium polyphosphate C8: Melamine resincoated ammonium
polyphosphate B1: Homopolymer of
2piperazinylene-4-morpholino-1,3,5-triazine B2: Homopolymer of
2piperazinylene-4-N,N-(2-hydroxyethyl)amino-1,3,5-triazine B3:
Copolymer of 2piperazinylene-4-morpholino-1,3,5-triazine in the
equimolar ratio B4: Reaction product of cyamuric chloride with
ethylenediamine (2:3) D1: PE copolymer [E content: 8.5 wt. %, MFR
(230.degree. C., 2.16 kgf): 2 g/10 min D2: LDPE [trade name:
PETROCEN 186, available from Toso Corp. D3: Polystyrene resin
[trade name: STYRON 475S, available from Asahi Chemical Industry
Co., Ltd. *: Caused by marked heat distortion in hot water E:
excellent, G: good, B: bad, W: worst
TABLE 4 ______________________________________ Component of
Flame-retardant Resin Composition Mean particle B C Amount diameter
B1 B2 C1 Kind % (.mu.m) % % % C2 C3
______________________________________ Ex.23 Magnesium 0.5 5.6 5 --
-- -- 17 oxide Ex.24 Aluminum 1.0 3.7 5 -- -- -- 17 oxide Ex.25
Magneisum 2.0 1.7 -- 5 -- -- 17 hydroxide Ex.26 Magnesium 1.0 5.6
-- 5 -- -- 17 hydroxide Ex.27 Magnesium 2.0 3.7 -- 5 -- -- 17
hydroxide ______________________________________ Flame Retardance
Component of Flame-retardant Oxygen Resin Composition Index UL D
(O.I.) 94V D1 D2 D3 Addit- 3.0 mm- 1.2 mm- % % % D4 D5 ives thick
thick ______________________________________ Ex.23 57.0 10 10 -- --
0.5 33.5 V-O Ex.24 56.5 10 10 -- -- 0.5 34.1 V-O Ex.25 55.5 10 10
-- -- 0.5 33.2 V-O Ex.26 56.5 10 10 -- -- 0.5 34.6 V-O Ex.27 55.5
10 10 -- -- 0.5 34.7 V-O ______________________________________ B1
and C1 are the same as in Table 1. B2: Product obtained by reacting
cyanuric chloride with ethylenediamine i the molar ratio of 2/3
(cyanuric chloride/ethylenediamine) C3: Waterinsoluble ammonium
polyphosphate D1, D2 and D3 are the same in Table 1.
TABLE 5 ______________________________________ Water-insoluble
Ammonium Polyphosphate Mean particle Diameter and Water- Molded
Article from soluble Content (wt. %) the Composition Mean Izod
Dupont Particle Temperature and Content Impact Impact Diameter (wt.
%) Strength Strength .mu.m 25.degree. C. 50.degree. C. 75.degree.
C. (kg.cm/cm) (10.degree. C.)
______________________________________ Ex.28 6.8 1.0 3.0 7.0 5.5 80
Ex.29 6.8 1.0 3.0 7.0 5.5 80 Ex.30 6.8 1.0 3.0 7.0 Ex.31 6.8
<0.1 0.5 1.5 Ex.32 6.8 <0.1 0.5 1.5 Ex.33 6.8 1.0 2.0 5.0
Ex.34 6.8 1.0 2.0 5.0 Ex.35 6.8 <0.1 0.7 3.5 Comp. 30 8.0 40 100
3.5 20 Ex.9 Comp. 30 1.2 3.8 24 3.5 20 Ex.10 Comp. 20 5.0 23 64
Ex.11 Comp. 6.8 1.7 7.3 58 Ex.12 Comp. 6.8 2.0 8.2 62 Ex.13 Comp.
6.8 1.4 4.8 36 Ex.14 Comp. 6.8 1.2 3.5 22 Ex.15 Comp. 6.4 18 51 100
Ex.16 Comp. 6.8 1.7 7.3 58 Ex.17
______________________________________
EFFECT OF THE INVENTION
The thermoplastic polymer composition of the invention containing a
flame retardant, which is prepared in accordance with the primary
flame retardance formulation and shows high flame retardance even
if the flame retardant is used in a small amount, exerts the
following effects.
(1) In spite of a low content of the flame retardant, the
flame-retardant polymer composition prepared in accordance with the
primary flame retardance formulation exhibits high flame
retardance.
(2) The flame-retardant polymer composition prepared in accordance
with the primary flame retardance formulation can provide favorable
materials used in fields of electrical appliances, building
industry, automobile parts, etc.
The flame-retardant polymer composition of the invention containing
water-insoluble ammonium polyphosphate (C3-C5) as a main flame
retardant, which is prepared in accordance with the secondary flame
retardance formulation, exerts the following effects.
(3) The molded article obtained from the flame-retardant polymer
composition prepared in accordance with the secondary flame
retardance formulation is remarkably improved in the bleed
resistance under the conditions of high temperature and high
humidity. (The bleed resistance was evaluated by variation of
resistance value in hot water immersion and a lasting period under
the conditions of high temperature and high humidity).
(4) The molded article obtained from the flame-retardant polymer
composition prepared in accordance with the secondary flame
retardance formulation is also improved in the flame
retardance.
(5) A decomposition gas is hardly generated not only when the
flame-retardant polymer composition prepared in accordance with the
secondary flame retardance formulation is molded into an article
but also when the molded article is exposed to flame.
(6) The molded article obtained from the flame-retardant polymer
composition prepared in accordance with the secondary flame
retardance formulation is suitable for electrical appliances.
(7) The molded article obtained from the flame-retardant polymer
composition prepared in accordance with the tertiary flame
retardance formulation exerts both effects by the primary flame
retardance formulation and the secondary flame retardance
formulation.
(8) According to the process of the invention, a water-insoluble
ammonium polyphosphate powder essential to the preparation of the
flame-retardant polymer composition of the secondary flame
retardance formulation can be readily obtained.
* * * * *